Compounds with liquid crystalline properties and coating binders based thereon

ABSTRACT

Polymeric vehicles with liquid crystalline-like properties, solvent dispersible polymeric vehicles, formulated coating compositions with liquid crystalline-like properties and a method for imparting liquid crystalline properties to a coating binder are described. The materials with liquid crystalline-like properties lack structural segments previously regarded as mesogenic.

This is a division of application Ser. No. 08/117,146, filed Sep. 13,1993, now U.S. Pat. No. 5,543,475, which is a 371 of PCT/US92/02155,filed Mar. 18, 1992, which is a continuation-in-part application of Ser.No. 07/672,537, filed Mar. 20, 1991, now abandoned.

This application relates to compounds with liquid crystalline (LC)-likeproperties and polymeric vehicles for coatings binders which includesuch LC-like compounds. More particularly, this application relates tocompounds with LC-like properties wherein parts or sections of thecompounds lack structural segments previously regarded as mesogenic. Thestructural segments of the compounds of the invention, however, providecertain properties that are similar to mesophases, but surprisinglythese structures have heretofore not been identified as mesogens.

BACKGROUND

The properties of liquid crystalline (LC)-polymers differ from those ofamorphous or crystalline polymers in ways that often have commercialvalue. Heretofore, the term "mesomorphous" has been synonymous with"liquid crystalline". LC polymers are known to form mesophases havingorder intermediate between crystalline polymers and amorphous polymers.See Flory, P. J., Advances in Polymer Science, Liquid Crystal PolymersI; Springer-Verlag; New York (1984) Volume 59; Schwarz, J. Mackromol,Chem. Rapid Commun. (1986) 1, 21. Further, mesophases are well known toimpart strength, toughness and thermal stability to plastics and fibersas described by Kwolek et al. in Macromolecules (1977) 10, 1390; and byDobb et al., Advances in Polymer Science, Liquid Crystal Polymers II/III(1986) 255(4), 179. Very recently it has been recognized that polymericnetworks made by cross-linking LC polymers and oligomers also havegreatly enhanced properties.

Because of their inherent scientific interest and of their many actualand potential commercial applications, LC polymers have been extensivelystudied. Many published studies have focused on identifying andclassifying the kinds of chemical structures that are associated withliquid crystallinity in polymers. These studies have led to formulationof a principle, which has been generally accepted: that liquidcrystallinity in polymers is invariably associated with the presence of"mesogenic groups". Mesogenic groups are chemical structures within thepolymer which are capable, in certain circumstances, of imparting liquidcrystallinity. Lengthy review articles cataloging and classifyingmesogenic groups have been written. Most commonly, mesogenic groups arechemical structures that contain a rigid sequence of at least twoaromatic rings connected in the para position by a covalent bond or byrigid or semi-rigid chemical linkages. Optionally, one of the rigidaromatic rings may be naphthalenic rings linked at the 1,5- or 2,6-positions. Of several broad classes of mesogenic groups, the most commoncontains two or more 1,4-arylene (or, less commonly,1,4-trans-cyclohexenyl) rings covalently connected by rigid orsemi-rigid linkages which include but are not limited to ##STR1## andvarious mesogens described in Ober et al., Liquid Crystal Polymers withFlexible Spacers in the Main Chain, Advances in Polymer Science 59, 104at 105-117 which is incorporated by reference herein.

Until recently the study of LC polymers as potential coatings bindershas received little attention. Chen et al., J. Coat. Technol. 1988, Vol.60 (756), p. 39 prepared alkyd resins with mesogenic polyp-hydroxybenzoic (PHBA) acid segments (a common LC monomer) pendant tothe polymer backbone. Improved dry times and film properties wereobserved for the alkyds. Chen et al., J. Appl. Polym. Sci. 1988, Vol.36, p. 141 also prepared LC acrylic polymers with pendant poly PHBAgroups that gave excellent lacquer and enamel properties. Wang et al.,Polym. Mater. Sci. Eng. 1987, 56, 645, prepared oligoester diols whichwere end-capped with PHBA units. Cross-linked enamels were prepared thatdisplayed excellent properties. Dimian et al., Polym. Mater. Sci. Eng.1987, 56, 640, synthesized LC oligomer diols based on the mesogen4,4'-terephthaloydioxydibenzoyl chloride. The LC diols were cross-linkedto give enamels with excellent properties.

Japanese patents have claimed that PHBA enhances the properties ofpolyester powder coatings; Japanese Kokai 75/40, 629 (1975) to Maruyamaet al.; Japanese Kokai 76/56/839 (1976) to Nakamura et al.; JapaneseKokai 76/44,130 (1976) to Nogami et al.; and Japanese Kokai 77/73,929(1977) to Nogami et al.

In classifying "mesogenic groups" one also, overtly or by implication,classifies other groups as "non-mesogenic". Such groups are chemicalstructures that are outside the boundaries of the various types ofmesogenic groups. They are generally considered incapable of impartingliquid crystallinity under any circumstances. Two types of non-mesogenicgroups are of particular interest: (1) single 1,4-arylene units that areconnected to other aromatic rings in the polymer structure by flexiblerather than rigid or semi-rigid linkages and (2) 1,3-arylene ringsconnected in any way. Examples type of (1) and groups derived fromterephthalic acid, hydroquinone and 4-hydroxybenzoic acid are: ##STR2##Examples of non-mesogenic groups of type (2) are those derived fromisophthalic acid, resorcinol and 3-hydroxybenzoic acid: ##STR3##

In a recent publication Kricheldor, Pakull and Buchner, Macromolecules,21, 1929-1935 (1988)! it was reported that a polymer containing twoelectronically different aromatic non-mesogenic groups is "liquidcrystalline". The structure of this polymer is: ##STR4## Krichedor etal. considered their finding very surprising. They explained theformation of liquid crystallinity by postulating a "special co-operativeeffect, presumably a charge-transfer interaction, between the aromaticmonomer units." They stated ". . . the mesophase of 4e (the aboveFormula 1) is formed despite the absence of mesogenic groups. Obviously,special interaction between the bisphenol and the benzophenone imideunit is responsible for the observed smectic phases. This interaction ismost likely a weak charge-transfer (CT) complexation." It was taken as agiven that the isolated bisphenol unit is not a mesogenic group whichmay be a matter of semantics when the resulting compound exhibitsLC-like properties. Indeed, semantically because the resulting compoundshave LC-like properties certain linkages or parts of the compounds maybe considered mesogens or mesogenic.

In another publication Bilibin, et al. Makromol. Chem., Rapid Commun. 6,209-213 (1985)! it was reported that chemical compounds of the structure##STR5## ". . . exhibit monotropic mesomorphism. This can be accountedfor by intermolecular hydrogen bonding as in the case of the4-alkoxybenzoic acid melt." Also see Fornasier et al. Liquid Crystals 8,787-796 (1990).

It is an object of this invention to provide polymeric vehicles forcoatings binders which have LC-like properties.

It is another object of this invention to provide a method of impartingLC-like properties to coatings binders.

It is still another object of this invention to provide solventdispersible polymeric vehicles for coatings binders which have LC-likeproperties.

It is yet another object of the invention to provide a method whichprovides polymeric vehicles with new thixotropic and anti-saggingproperties.

Still further objects and advantages of the invention will be found byreference to the following description.

SUMMARY OF THE INVENTION

In this invention new polymeric vehicles with LC-like properties,solvent dispersible polymeric vehicles and formulated coatingcompositions with LC-like properties and a method for imparting liquidcrystal-like properties to a coating binder and a method for providing apolymeric vehicle with thixotropic and anti-sagging properties have beendiscovered. The method and new polymeric vehicles of the inventionprovide coating binders with LC-like properties; and as a result, themethod and polymeric vehicle of the invention provide coating bindersand coatings with improved properties including hardness and impactresistance heretofore generally associated with known mesogenic groupsand known LC polymers in the polymeric vehicle.

When applied to a substrate, some of the polymeric vehicles of theinvention having LC-like properties, provide coating binders having apencil hardness of at least about 3H and a reverse impact resistance ofat least about 60 inch-lbs. at a binder thickness of about 1 mil. In oneaspect of the invention, the polymeric vehicle comprises a dispersiblepolyester having the general Formula I shown below or dispersibleadducts of the polyester having the general formula shown below:##STR6## As used herein the term "dispersible" means that the polyesterof the general formula or the adducts (amine salts or mono-oxiraneaddition products) of that polyester are dispersible in a medium at 25°C. which medium may also include a dispersant. The medium for thedispersion may be water, organic solvent, cross-linking agent, reactivediluent and may be or include the adducts of the polyester of generalFormula I. The adducts of the polyester of Formula I also may act as adispersant as well as serve as the medium. While the term "polyester" isused in connection with the compounds of the general formula, thecompounds defined by the above general formula have molecular weights ofless than about 10,000, and as a result, are oligomers.

In another aspect of the invention, the polymeric vehicle of theinvention comprises adducts of the hydroxyl or carboxyl terminatedpolyester with the above general formula and a cross-linking agent in anamount effective for cross-linking the polyester to provide the coatingbinder. Many of polyesters which form part of the polymeric vehicle ofthe invention are not dispersible in solvents commonly used inconnection with coatings. When there is a predominately aqueous media,to achieve solvent dispersibility, polymers which form a part of thepolymeric vehicle of the invention are made water reducible byconverting the polymers into salts (such as amine salts) by reacting abase (such as an amine) with the polyesters having acid functionality.In this aspect of the invention, a polyester having the above generalformula which is a diol is converted into a diacid, tri or tetracid witha polyfunctional acid or anhydride thereof having from 4 to 20 carbonatoms. This conversion provides a carboxylated polyester or a partlycarboxylated polyester where all of the hydroxy groups on the polyesterhave not been reacted with an acid or anhydride. In this aspect of theinvention, the polyester of the general formula is reacted with at leastabout 10 percent and preferably 25 percent of the stoichiometric amountof acid or anhydride required to carboxylate all of the hydroxyls of thediol polyester of general formula to provide a carboxylated polyester.When the carboxylated polyester is combined with a base, such as anamine, it forms a water dispersible salt. This provides waterdispersibility of the polyester and polymeric vehicle of the invention.Preferably the base has a boiling point of less than about 200° C.

In another aspect of the invention, dispersibility of the polymericvehicle of the invention in organic solvents is effected (1) by graftinga mono-oxirane having not more than 25 carbon atoms onto the polyesterof the above general formula to provide a modified polyester which isdispersible in organic solvents in a non-aqueous media or (2) bydispersing the polyester of the above general formula in a reactivediluent in combination with the organic solvent. Broadly the reactivediluent is a hydrocarbon organic liquid having from about 2 to about 5,preferably 2, functional groups such as carboxyl and hydroxyl,preferably hydroxyl. Through its functional groups, the reactive diluentis capable of reacting with the cross-linking agents described herein(preferably an aminoplast or polyisocyanate) and has a viscosity at 25°C. of from about 0.5 Pa.s to about 25 Pa.s. By way of example, thereactive diluents may be a reaction product of (1) an aromatic hydroxyacid or diacid such as terephthalic acid, para hydroxy benzoic acid or2,6-naphthalenic acid with a mono-oxirane having not more than 25 carbonatoms such as the oxiranes described in connection with making amodified polyester by grafting a mono-oxirane thereon or (2) is thereaction product of a straight chain aliphatic diacid having 4 to 14carbon atoms with the cyclohexyl diol 1,4-dimethyiol cyclohexane whichhas the structure ##STR7## or is the reaction product of 1,6-cyclohexanedicarboxylic acid with a straight chain diol having 4 to 14 carbonatoms.

In the aspect of the invention which includes grafting the mono-oxiraneonto the polyester to provide a modified polyester, the modifiedpolyester is the reaction product of the mono-oxirane, the mono-oxiranebeing in an amount effective for making the polyester dispersible in anorganic solvent. In this aspect of the invention, if the polyester ofthe general formula is a polyol such as diol, that diol first is reactedwith a polyfunctional carboxylic acid or anhydride, having from about 4to 20 carbon atoms as described above, to carboxylate the diol polyester(and make it a carboxylated polyester) prior to reacting the polyesterwith the oxirane to graft it onto the polyester. The modified polyesterwith the oxirane grafted thereon may be dispersed into an organicsolvent medium by itself or as a part of a blend of modified polyesterand polyester of the general formula. The modified polyester in theblend is in an amount effective for making the blend dispersible in anorganic solvent which amount is a function of the solvent and the amountof oxirane grafted onto the polyester. In general for a polyester whichhas been reacted with a stoichiometric amount of oxirane, the blend ofpolyester and modified polyester will include at least about 70 weightpercent and preferably at least about 80 weight percent modifiedpolyester in dispersions having at least about 50 weight percentpolyesters (both modified and unmodified polyester).

In the aspect of the invention which uses the reactive diluent asopposed to the modified polyester, the reactive diluent may be used todisperse carboxylic polyesters without hydroxy groups, but hydroxypolyesters are preferred. In addition to using organic solvents as themedia for such dispersion, the reactive diluent may be used as a part ofthe media or function as a dispersant in such dispersions. Stablenonaqueous dispersions of hydroxy polyesters, such as diol polyesters ofthe general formula are formed at polyester to diluent ratios of fromabout 10:1 to about 1:4 and preferably from about 4:1 to about 1:4 atsolids levels of from about 40 to about 80 weight percent. Thesedispersions provide a formulated coating composition which includes thepolyester of the general formula, cross-linking agent, reactive diluent,and in and a preferred aspect a second dispersant additional to thereactive diluent and optionally organic solvent as an additional medium.While not intending to be bound by any theory, in the aspect of theinvention which includes the reactive diluent with the polymeric vehiclein a nonaqueous media, it is believed that sometimes the reactivediluent associates with both the polyester of the general formula andsolvent. This association coupled with the bulky structure of thereactive diluent results in steric stabilization. Additionally, thereactive diluent is di- or polyfunctional which functionality allowscross-linking by polyisocyanate and melamine resins during the curing ofthe polymeric vehicle into a coating binder.

Without using polyesters with mesogens or groups thought to bemesogenic, the invention also provides a method of imparting liquidcrystalline properties to a coating binder with resulting, in certaincases, improved hardness and impact resistance associated with liquidcrystalline polymeric vehicles. This method includes mixing a polyesterwithout mesogens or groups which impart L/C properties, a modifiedpolyester or adducts of the polyester of the general formula with across-linking agent to provide, in some cases, a polymeric vehicle or aformulated coating composition which will provide a resulting coatingbinder having a pencil hardness of at least 3H and a reverse impactresistance of at least about 60 inch-lbs. at a binder thickness of about1 mil.

The invention provides polymeric vehicles and formulated coatingcompositions with "non Newtonian" viscosities and rheological propertieswhich are well suited for polymeric vehicles for paint coatings. Theinvention provides compositions which have high viscosities at low shearrates, viscosities of at least about 15 Pa.s at shear rates of notgreater than 1,000 sec⁻¹ in the temperature range of from about 25° C.to about 60° C., but low viscosities at high shear rates, viscosities ofnot greater than 5 Pa.s at shear rates of at least about 3,000 sec⁻¹ inthe temperature range of from about 25° C. to about 60° C. Moreover, theinvention provides polymeric vehicles and formulated coatingcompositions which have a viscosity which increases when the temperatureof the polymeric vehicle is raised such as raised above about 25° C. forcuring. Such properties are well suited for polymeric vehicles forcoating binders for paint. Low viscosities at high shear rates provide acoating composition which can be readily applied by means which providefor high shear rates: spraying, rolling or brushing. Moreover, theinvention provides for the design of polymeric vehicles and formulatedcoating compositions which thicken and increase in viscosity at criticalbake or cure temperatures as the polymeric vehicle is heated above 25°C. This avoids oven sagging of the coating composition during curing attemperatures higher than ambient. Oven sagging is a common problem formany enamels due to a dramatic drop in viscosity at higher temperatures.The invention provides a polymeric vehicle which has a viscosity whichincreases with temperature in certain temperatures ranges until amaximum; as a result, the viscosity is sufficiently high at bakingtemperatures to minimize sagging.

Besides the latter special viscosity-vs-temperature behavior, thepolymeric vehicles of the invention are thixotropic as well as shearthinning and exhibit yield stress below a certain temperature (such asT_(m) /T_(c)). While thixotropic compositions are not new, the extent of"shear thinning" permitted by the invention in polymeric vehicles of theinvention is novel and has not been heretofore observed in polymericvehicles comprising oligomeric mixtures which are substantially free ofpolymers having molecular weights greater than about 10,000. Thethixotropic and yield-stress properties of the polymeric vehicles of theinvention enhance the anti-sagging properties of the formulated coatingsof the invention, since they will allow lower viscosity at applicationconditions (such as brushing, rolling, and spraying) while remaining ata higher viscosity at baking condition (without pre-shearing or at lowershearing force). While higher viscosity during curing is good foranti-sagging, it may lead to poor levelling. Thus, an intermediateviscosity should be chosen for formulated coating compositions in orderto obtain both good levelling and sagging resistance. This can beachieved by adjusting the curing temperature or the type and amount ofsolvent around the viscosity maximum.

The polyester of the invention is the reaction product of an aromaticcompound selected from the group consisting of (I) a 1,4-disubstitutedbenzene which has hydroxyl or carboxylic substitution such asterephthalic acid, hydroquinone, (II) a 2,6-disubstituted naphthalenewhich has hydroxyl or carboxylic substitution, such as 2,6-dihydroxy- ordicarboxy naphthalene, and (III) mixtures thereof with a linear diacidor diol having 6 to 17 carbons and 4 to 15 methylene groups. Thelinearity of the acid or diol co-reactant provides flexible spacergroups between aromatic groups; yet, surprisingly, the polymeric vehicleof the invention has LC-like properties.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The polyesters of Formula I as a part of a dispersible polymericvehicle, including but not limited to being dispersible in an aqueous ororganic solvent media, amino salt adducts thereof, oxirane adducts ofthe hydroxyl and carboxyl terminated polyester of Formula I and blendsaccording to the invention may be used to make a polymeric vehicle or aformulated coating for a coating binder for improved properties such aswould be expected in polymeric vehicles with known mesogenic groups. Incertain aspects of the invention, some of the polymeric vehicles of theinvention provide coating binders having a pencil hardness at leastabout 3H and a reverse impact resistance of at least about 60 inch-lbs.at a binder thickness of about 1 mil.

The polymeric vehicle of the invention includes cross-linking agentswhich react with the polyester of the general Formula I, amine saltsthereof or oxirane adducts of carboxyl or hydroxyl terminated polyestersof Formula I to provide a coating binder which has a reverse impactresistance of at least about 60 inch-lbs. and a pencil hardness of atleast about 3H. The cross-linking agent has a functionality of two ormore, that is, it contains at least two and preferably three or morereactive groups; examples are polycarboxylic acids, polyols, aminoplastresins, polyisocyanate resins such as the trimer of toluenediisocyanate,hexamethylene diisocyanate (HMDI) and a biuret thereof, isophronediisocyanate (IPDI), isocyanates and mixtures thereof. The aminoplastresin may be a melamine resin, such as hexakis (methyloxymethyl)melamine resin (HMMM). The polyisocyanate resin may be a blockedpolyisocyanate resin which is blocked with active hydrogen compoundssuch as alcohols, phenols, oximes or lactams.

Solvents and known additives such as pigments may be added to thepolymeric vehicle to provide a formulated coating composition which is adispersion. In the aspect of the invention which provides a polymericvehicle for a coating binder, the coating binder gives a coating filmwith high hardness, flexibility, and impact resistance heretoforeassociated only with polymeric vehicles which include known mesogens.After the formulated coating is applied to a base or substrate, solvents(if present) evaporate leaving a solvent-free film. Evaporation andcross-linking may be accelerated by heating, as by baking. An improvedfilm provided by the polymeric vehicle with improved hardness,flexibility and impact resistance, and the coating binder therefor, area particularly important part of this invention. Moreover, an importantaspect of this invention is that the raw materials for the polymericvehicle are inexpensive and readily available. Since the coating binderprimarily provides the desired film characteristics, the properties ofthe coating binder are particularly described primarily by tests whichmeasure hardness and impact resistance.

Definitions

As used in this application, "polymer" means a polymer with repeatingmonomeric units as defined by the general formula and includes oligomersas defined herein. "Polyester" means a polymer which has ##STR8##linkages in the main chain of the polymer. "Oligomer" means a compoundthat is a polymer, but has a number average weight not greater thanabout 10,000 with repeating monomeric units. "Adduct of the polyester"means the following chemical addition products of the polyester of thegeneral formula I: (1) the amine salt of acid polyester of generalFormula I or of the carboxylated hydroxyl terminated polyester ofgeneral Formula I; and (2) a mono-oxirane bonded onto the polyester ofthe general Formula I or onto the carboxylated hydroxyl terminatedpolyester of general Formula I. "Cross-linking agent" means a di- orpolyfunctional substance containing functional groups that are capableof forming covalent bonds with hydroxyl and carboxyl groups that arepresent on the polymer; aminoplast and polyisocyanate resins are membersof this class; melamine resins are a sub-class of aminoplast resins."Modified polyester" means a polyester having covalently bound modifyingmono-oxirane groups as described herein and the term "grafted" or"grafting" used herein in connection with mono-oxiranes means that suchoxiranes are covalently bound to the polyester; that is, the oxiraneadduct is made in a process of adding the oxirane to an existingpolyester. "Polymeric vehicle" means all polymeric and resinouscomponents in the formulated coating, i.e., before film formation,including but not limited to modified polymers. The polymeric vehiclemay include a cross-linking agent and reactive diluent as describedherein. "Coating binder" means the polymeric part of the film of thecoating after solvent has evaporated and after cross-linking."Formulated coating" means the polymeric vehicle and solvents, pigments,catalysts and additives which may optionally be added to impartdesirable application characteristics to the formulated coating anddesirable properties such as opacity and color to the film.

"Solvent" means water and/or an organic solvent.

"Organic solvent" means a liquid which includes but is not limited tocarbon and hydrogen which liquid has a boiling point in the range offrom about 35° C. to about 300° C. at about one atmosphere pressure.

"VOC" means volatile organic compounds and "low VOC" means about 1 poundper gallon or about 120 grams of volatile organic compounds per liter offormulated coating composition, not including water. "Volatile organiccompounds" are defined by the U.S. Environmental Protection Agency asany organic compound which participates in atmospheric photochemicalreactions, except for specific designated compounds which havenegligible photochemical activity. Water and CO₂ are not VOCs. VOCs havebeen generally designated to include but are not limited to myrcene,cumene, butyne, formaldehyde, carbon tetrachloride, aniline,dimethylnitrosamine, formic acid, acetone, chloroform, hexachloroethane,benzene, trichloroethane, methane, bromoethane, ethane, ethene,acetylene, chloromethane, iodomethane, dibromomethane, propane,1-propyne, chloroethane, vinyl chloride, acetonitrile, acetaldehyde,methylene chloride, carbon disulfide, thiobismethane, bromoform,bromodichloromethane, 2-methylpropane, 1,1-dichloroethane,1,1-dichloroethene, phosgene, chlorodifluoromethane,trichlorofluoromethane, dichlorodifluoromethane, tetrafluoromethane,tetramethylplumbane, 2,2-dimethylbutane, monomethylester-sulphuric acid,dimethylbutanone, pentachloroethane, trichloro-trifluroethane,dichlorotetrafluoroethane, hexachlorocyclopentadiene, dimethyl sulfate,tetraethylplumbane, 1,2-dibromopropane, 2-methylbutane,2-methyl-1,3-butadiene, 1,2-dichloropropane, methyl ethyl ketone,1,1,2-trichloro ethane, trichloroethene, 2,3-dimethylbutane,tetrachloroethane, dimethyl-3-methylene-bicyclo-heptane, A-pinene,hexachloro-butadiene, methylnaphthalene, naphthalene, quinoline,methylnaphthalene, phenyl-propanone, dimethylbenzene, O-cresol,chloro-methylbenzene, dichlorobenzene, trimethylbenzene,tetramethylbenzene, dibromo-3-chloropropane, 3-methylpentane,3-pentanone, methylcyclopentane, (1-methylethyl)-benzene,1-(methylethenyl)-benzene, 1-phenylethanone, nitrobenzene,methylmethylethyl-benzene, ethylbenzene, ethenylbenzene, benzychloride,benzonitrile, benzaldehyde, propylbenzene, butylbenzene,1,4-diethylbenzene, 2,4-dimethylphenol, dimethylbenzene,chloro-methylbenzene, dichlorobenzene, dibromoethane, 3-bromo-1-propene,butane, 1-butene, 1,3-butadiene, 2-propenal, bromochloroethane,1,2-dichloroethane, propanenitrile, 2-propenenitrile, 2-methylpentane,2-pentanone, 2,4-dimethylpentane, 1,3-dimethylbenzene, m-cresol,2,4-dimethylpyridine, 2,6-dimethylpyridine, trimethylbenzene,dimethylphenol, trichloro-benzene, trimethyl-pyridine, bromobenzene,methylcyclohexane, toluene, chlorobenzene, phenol, 2-methylpyridine,pentene, 2-pentane, bromo-chloropropane, 1H-pyrrole, tetrahydrofuran,hexane, 1,4-dichlorobutane, cyclohexane, cyclohexene, pyridine, octaine,1-octene, nonane, dodecane, propene, 2-methyl-1-pentene,2-methyl-1-propene, isoquinoline, trichlorobenzene, propanal, butanal,1,4-(dioxane), 1-nonene, decane, dibromochloromethane,2-chloroburadiene, tetrachloroethene, dimethyl-methylenebicyclo-heptane,1,2-diethylbenzene, (1-methylpropyl)-benzene, Acetic Acid ethyl-ester,1,3-diethylbenzene, cyclopentene, heptane, cis-dichloroethene,trans-dichloroethene, cyclopentane, cycloheptane, 1,2-propadiene, carbonoxide sulfide, 2,2,3-trimethylbutane, tetramethylbenzene,2,4,5-trimethylphenol, 2-methyl-2-butene, tetramethylbenzene,2,4,6-trimethylphenol, pentylbenzene, trimethyl-pentane,decamethylcyclo-pentasil-oxane, 1,3-dichlorobenzene, hexadecane,2-methylthiophene, 3,3-dimethylpentane, 3-methyl-2-butene,2-methyl-1-burene, 2,2,3-trimethyl-pentane, 2,3-dimethylpentane,2,3,4-trimethylpentane, 2,6-dimethylphenol, 1,2,3-trimethylbenzene,2,3-dimethylpyridine, 2,3-dimethylhexane, 3-chlorobenzaldehyde,3-methylhexane, 2,4-dimethylhexane, 3-methylheptane, (Z)-2-butene,2-methylhexane, trimethylbicyclo-heptane, (E)-2-heptene, 4-methylnonane,tetrachlorobenzene, butene, chloronitrobenzene, dichlorobenzene,dichloroethene, tetramethyl benzene, bromopropane, dichloro-1-propene,chlorobenzenamine, dimethylcyclohexane, dichloronitrobenzene,dichloronaphthalene, dimethylcyclopentane, bromoethylbenzene,dichloromethyl-benzene, benzenedicarboxaldehyde, benzoyl nitro peroxide,bromochloropropane, dibromo-chloro-propane, pentachlorobutadiene,dibromochloropropane, 2-butoxyethanol, bromopentachloro ethane,tetradecamethylcycloheptasiloxane, trimethyl-pentanediol,dodecamethylcyclo-hexasil-oxane, hexamethylcyclotri-siloxane,octamethylcyclo-tetrasil-oxane, hexadecamethylcyclooctasil-oxane,tridecane, tetradecane.

A "high solids formulated coating composition" means a nonaqueousformulated coating containing not more than about 400 grams of volatileorganic substances per liter of formulated coating composition andpreferably less than about 300 grams of VOCs per liter of formulatedcoating composition. "Film" is formed by application of the formulatedcoating to a base or substrate, evaporation of solvent, if present, andcross-linking. "Air-dried formulated coating" means a formulated coatingthat produces a satisfactory film without heating or baking. "Bakedformulated coating" means a formulated coating that provides optimumfilm properties upon heating or baking.

Although many of the polymers and copolymers exhibit LC-like properties,the criteria for liquid crystallinity is varying. The X-ray structureanalysis can in certain instances prove liquid crystallinity, but suchanalysis is costly and the results are sometimes ambiguous. Less costlytechniques are widely used to gain evidence for the presence of liquidcrystallinity and to study it. The most common are

polarizing microscopy,

differential scanning calorimetry (DSC),

dynamic mechanical-thermal analysis (DMTA),

wide angle X-ray scattering (WAXS), and

rheological studies.

The quality of evidence of liquid crystallinity obtained from suchstudies may range from quite convincing to highly questionable in agiven instance. Often a single technique, such as polarizing microscopyor DSC, can provide very strong, if not absolutely unchallengeable,evidence that a given polymer is liquid crystalline.

Given the above situation, applicants do not necessarily assert thepolymers, polyesters and adducts thereof and polymeric vehicle of theinvention are liquid crystalline. They may be, but rather, applicantsassert that the polymers, polyesters and adducts thereof and polymericvehicle of the invention exhibit liquid crystalline-like properties, oralternatively provide a polymeric vehicle with desired hardness andimpact resistance. As used herein a composition or polymer exhibitsliquid crystalline-like or liquid crystalline properties if at minimum asubstantially homogeneous compound or polymer displays first ordertransitions at two different temperatures by DSC.

Hydroxyl Terminated Polyesters of The General Formula--NonaqueousSystems

Broadly in one aspect of the invention, the hydroxyl terminatedpolyester of Formula I is dispersed in a media such as a mono-oxiraneadduct of the polyester of the general Formula I, an organic solvent andcross-linking agent with a dispersant such as a nonionic surfactant orlecithin to provide a formulated coating composition which providesunique coating binders with properties as previously described. Thecross-linking agent is required and is in an amount effective forproviding the coating binder and the media is in an amount effective forproviding the dispersion for a low VOC formulated coating composition.Dispersants may or may not be required to complete or stabilize thedispersions.

In one aspect of the invention using an organic solvent as a part of alow VOC nonaqueous formulated coating composition, the polymeric vehicleof the invention comprises a cross-linking agent together with fromabout 20 to about 92 weight percent, based upon the weight of the weightof the polymeric vehicle, of an organic solvent dispersible oxiraneadduct of a hydroxyl terminated polyester having LC properties andhaving the general Formula I: ##STR9##

The above polyester is hydroxyl terminated where ##STR10## andAl'=(CH₂)_(n) or bond and ##STR11## or bond, but if Al'=bond then##STR12## or bond and if Ar=bond then ##STR13## or bond. The remainderof the polymeric vehicle optionally may comprise other polyesters.Cross-linking agents which may be used in such nonaqueous systems areaminoplasts, amines, regular and blocked di- and polyisocyanates andepoxies.

The hydroxyl terminated polyesters of the above general formula such as##STR14## have low or no dispersibility in most common organic solvents,such as xylene or toluene. According to the invention, however, thesehydroxyl terminated polyesters may be modified with a mono-oxiranehaving not more than 25 carbon atoms to provide an oxirane adduct of thepolyester, which modified polyester (or adduct) is dispersible inorganic solvents. The polyester modified to the oxirane adduct may beused either alone or as a blend with the polyester of the generalformula along with a cross-linking agent to provide a polymeric vehiclewhich is dispersible such as in an organic solvent. The blend whichincludes the polyester, modified polyesters and cross-linking agent areparticularly important in providing polymeric vehicles which are a partof a high solids formulated coating composition.

In making the oxirane adduct of hydroxyl terminated polyesters, it ispreferable to first carboxylate the hydroxyl terminated polyester andthen react it with the oxirane as described in other portions of thisspecification. This is an adduct of the polyester of general Formula Iaccording to the invention.

In another important aspect of the invention, hydroxyl terminated ordiol polyesters of the general formula can be part of non-aqueousdispersions including high solids coating dispersions by combining thediol polyester with a reactive diluent. Broadly the reactive diluent isa hydrocarbon organic liquid having from about 2 to about 5, preferably2, functional groups such as carboxyl and hydroxyl, preferably hydroxyl.Through its functional groups, the reactive diluent is capable ofreacting with the cross-linking agents described herein (preferably anaminoplast or polyisocyanate) and has a viscosity at about 25° C. offrom about 0.5 Pa.s to about 25 Pa.s. The reactive diluent includes areaction product of (1) an aromatic hydroxy acid or diacid such asterephthalic acid, para hydroxy benzoic acid or 2,6-naphthalenic acidwith a mono-oxirane having not more than 25 carbon atoms such as theoxiranes described in connection with making a modified polyester bygrafting a mono-oxirane thereon, or (2) the reaction product of astraight chain aliphatic diacid having 4 to 14 carbon atoms with thecyclohexyl diol 1,4-dimethylol cyclohexane which has the structure##STR15## or the reaction product of 1,6 cyclohexane dicarboxylic acidwith a straight chain diol having 4 to 14 carbon atoms. In the case ofthe aromatic acid, the oxirane and the aromatic acid such asterephthalic acid are reacted in stoichiometric amounts with heating anda catalyst such as triphenyl benzyl phosphonium chloride (TPBPC). Whilenot intending to be bound by any theory, mono-oxiranes having bulkierstructures such as ##STR16## as will be further described herein providea diluent which appears to stabilize the dispersion through stericstabilization. In this connection a particularly useful diluent is thereaction product of terephthalic acid and a mono-oxirane sold under thename of Glydexx N-10 from Exxon Chemical Company. The reactive diluentalso appears to be capable of association with the polyester and solventfor further stabilization. Moreover, the reactive diluent isdifunctional which permits it to participate in the cross-linkingreaction of the polyester and cross-linking agents such as melamines andpolyisocyanates during curing. The dispersions formed with the reactivediluent and diol polyesters of the general formula are stable at solidslevels of from about 40 to about 80 weight percent.

Where reactive diluent is used as a part of dispersions according to theinvention, polymeric vehicles comprise the hydroxyl terminated polyesterof the general formula together with amounts of reactive diluent andcross-linking resins in amounts effective for providing a coating binderhaving a pencil hardness of at least about 3H and a reverse impactresistance of at least about 60 inch-lbs. at a binder thickness of 1mil. Generally, where reactive diluent is used the polymeric vehiclewill have at least about 10 weight percent and preferably at least about25 weight percent of the reactive diluent. Dispersants such as lecithin,a nonionic surfactant, or adduct of the polyester of Formula I togetherwith organic solvents also may be added to the formulated coatingcomposition to stabilize the system.

Hydroxyl Terminated Polyesters Of The General Formula--Aqueous Systems.

In yet another aspect of the invention where the polyester is hydroxylterminated or a diol, that polyester may be made dispersible in anaqueous solvent. To disperse the hydroxyl terminated polyester in anaqueous system, the hydroxyl terminated polyester of the general formulais carboxylated with a polyacid or anhydride, the anhydride beingpreferred, with a stoichiometric amount or less of the acid or itsanhydride. In a particularly important part of this aspect of theinvention, from about 10 to about 50 mole percent of the stoichiometricamount (the amount of acid or anhydride that would be required to haveone acid or arthydride molecule react with each available hydroxyl onthe polyester) of polyacid is particularly effective in providing thecarboxylated polyester having an acid value in the range of at leastabout 30 to provide water dispersibility after the polyester isconverted into an amine salt. The polyester may be carboxylated withtrimellitic arthydride, phthalic, succinic and maleic anhydrides orpolyacids such as adipic and isophthalic acid with trimellitic anhydridebeing preferred.

In this aspect of the invention, the amine salt of the carboxylatedhydroxyl terminated polyester of the general formula will provide awater dispersible polymeric vehicle which comprises a cross-linkingresin reactive with the amine salt of the carboxylated polyester. Theamine salt comprises from about 20 to about 92 weight percent, basedupon the weight of the polymeric vehicle, of the water dispersible aminesalt of the carboxylated polyester. The cross-linking agent in thepolymeric vehicle is an amount effective for crosslinking thecarboxylated polyester to provide a coating binder having a pencilhardness of at least about 3H and a reverse impact resistance of atleast about 60 inch-lbs. at a binder thickness of 1 mil. Generally, thecross-linking agent will comprise at least about 10 to about 50 weightpercent of the polymeric vehicle. Crosslinking agents which may be usedin the aqueous system generally are the same as those used in theaqueous system except that unblocked isocyanates can not be used in theaqueous system and blocked isocyanates can be used only with difficultyin an aqueous system.

Carboxyl Terminated Polyesters Of The General Formula--Aqueous Systems.

In another aspect of the invention the carboxyl terminated polyester ofthe above general formula permits a water dispersible polymeric vehicle.In this aspect of the invention, the polymeric vehicle comprises across-linking agent together with about 20 to about 92 weight percent,based upon the weight of the polymeric vehicle, of an aqueous solventdispersible polyester which is the amine salt adduct of the acidterminated polyester of the above general formula. This amine saltpolyester has LC properties and provides a coating binder having apencil hardness of at least about 3H and a reverse impact resistance ofat least about 60 inch-lbs. at a binder thickness of 1 mil. In thisaspect of the invention, the general Formula I defines the acidterminated polyester where V and ##STR17## or where V, Ar', Al' and Zall are covalent bond then ##STR18## In this aspect of the invention,the remainder of the polymeric vehicle may optionally comprise otherwater dispersible polyesters or amine salts thereof. As previouslystated, cross-linking agents which may be used in this aqueous systemare generally the same as those used in the nonaqueous system exceptthat unblocked isocyanates can not be used in an aqueous system and evenblocked isocyanates are used only with difficulty in an aqueous system.The cross-linking agent is used in an amount effective for providing thecoating binder with the hardness and impact resistance as previouslydescribed.

Carboxyl Terminated Polyesters Of The General Formula--NonaqueousSystems.

Broadly in one aspect of the invention as to the carboxyl terminatedpolyester of the general Formula I, these polyesters are dispersed in amedia such as a mono-oxirane adduct of the polyester of the generalFormula I, an organic solvent and cross-linking agent with a dispersantsuch as lecithin or a nonionic surfactant to provide a formulatedcoating composition which will give a coating binder with properties aspreviously described. The cross-linking agent may form part of the mediaand is in an amount effective for providing the coating binder, and themedia is in an amount effective for providing the dispersion for a lowVOC formulated coating composition. Dispersants may or may not berequired to complete or stabilize the dispersions.

In an important aspect of the invention, to make the acid terminatedpolyester of the general formula dispersible in many nonaqueous systems,it is reacted with the mono-oxirane having not more than 25 carbon atomswith heating to form a modified polyester which is an oxirane adduct ofsuch polyester. (If the polyester of the general formula is hydroxylterminated, the carboxylated form thereof, e.g. is made with apolycarboxylic acid or anhydride such as trimellitic, phthalic, succinicand maleic anhydride with trimellitic anhydride. This carboxylated formis reacted with the oxirane to form such adduct.) In connection withgeneral Formulas II and III, set forth infra, the hydroxyl terminatedpolyesters may be carboxylated to an acid value in the range of fromabout 5 to about 230. Thereafter the carboxylated polyester is reactedwith the mono-oxirane. The oxirane adduct of the acid resin aspreviously described with nonaqueous systems including the mono-oxiraneadduct of the hydroxyl terminated polyesters.

The Mono-Oxirane Adduct Aspect Of The Invention

The invention contemplates dispersions of or which include themono-oxirane adducts of the polyester of Formula I as formulated coatingcompositions. The medium for the dispersion may include the mono-oxiraneadduct, reactive diluent, cross-linking agent or organic solvents. Themono-oxirane reacted with a carboxyl terminated polyester or thehydroxyl terminated polyester (which is carboxylated prior to reactionwith the mono-oxirane) may be propylene oxide, ethylene oxide, butyleneoxide, phenylglycidyl ether, butylglycidyl ether, styrene oxide or theglycidyl esters of C-6 to C-22 mono acids. A particularly useful oxiranein the invention is a glycidyl ester of a C-10 oxo acid represented bythe general formula ##STR19## where R represents a mixture of aliphaticgroups, the three R groups in the oxirane having a total of 8 carbonatoms. That oxirane is commercially available from Exxon ChemicalCompany under the name of Glydexx N-10.

The amount of mono-oxirane grafted onto either of the carboxyl orhydroxyl terminated polyester of the general formula will vary fromabout 0.2 to about 2.0 or more moles of oxirane per mole of polyester,but the amount of mono-oxirane used should be effective for making thepolyester of the general formula dispersible such as in non-aqueousorganic solvents such as hydrocarbon solvents, aromatic solvents, estersand ketones. In general at 25° C., the modified polyester will compriseat least about 10 mole percent and preferably from about 25 to about 50mole percent of the oxirane radical bonded onto the polyester. Highmole-cular weight aliphatic oxiranes are more efficient dispersingagents in aliphatic solvents. The modified polymer may be designed withthe oxirane to disperse in less expensive hydrocarbon solvents which aremore likely to effect dispersion of modified polyesters with long chainoxiranes. Long chain oxiranes may adversely affect liquid crystalline orother properties which will cause the use of a shorter chain oxirane anda shift to a stronger solvent such as an aromatic or ketone. Theinvention contemplates the use of solvent blends and even the use ofmore than one oxirane to make the modified polymer.

The modified polyester which has mono-oxirane grafted thereon may be amedia for a dispersion of the polyesters of general Formula I (asopposed to the adducts thereof) together with cross-linking agent. Themodified polyester which has the mono-oxirane grafted thereon also maybe dispersed in a nonaqueous solvent media by itself or may be mixedinto a blend with an unmodified polyester of the general formula wherethe amount of modified polyester is effective to disperse all of thepolymeric vehicle of the blend into the solvent. For a polyester of thegeneral formula which has been reacted with a stoichiometric amount ofmono-oxirane, the blend of polyester and modified polyester will includeat least about 70 weight percent and preferably at least about 80 weightpercent modified polyester in dispersions having at least about 50weight percent modified and unmodified polyester.

Blending The Polyesters With Other Resins.

As described above, polyesters of the general Formula I or amine oroxirane adducts of these polyesters may be dispersed with otherpolyesters or other coating resins such as epoxy resins, e.g. thecarboxyl terminated polyester with a poly functional epoxy resin whichserves as a cross-linking agent. In the blends which include polyfunctional epoxy resins, the oxirane adduct will comprise from about 5to about 20 mole percent of the polymeric vehicle. In organic solventsystems, the oxirane adduct of the polyesters may be dispersed withother resins reactive with such adduct to provide a polymeric vehiclewith L/C-like properties. In aqueous solvent systems, the amine saltadduct of the polyesters of the general formula may be blended withother water dispersible resins reactive with such amine salt adduct toprovide a polymeric vehicle. In these circumstances, to maintain theliquid crystalline characteristics of the polymeric vehicle, if theother resins are not liquid crystalline, a minimum of about 30 weightpercent, and preferably about 50 weight percent of the polymericvehicle, based upon the weight of the polyester of the general formulaor such polyester as a part of any adduct thereof, i.e. the weight inthe latter instance would not include the weight of the mono-oxiraneportion of the polyester. This will provide a polymeric vehicle whichwill result in a coating binder with a hardness and impact resistance aspreviously described.

Specific Important Polyesters As A Part Of The Invention

Polyesters having the general Formulas II, III, IV and V are importantaspects of the invention as follows.

The oxirane adducts of Formulas II or III or Formulas II or III as partof the previously described reactive diluent are particularly importantaspects of the invention. ##STR20##

The amine acid salt and the oxirane adducts of Formulas IV and V areparticularly important aspects of the invention where the polyesters arecarboxyl terminated. ##STR21##

Making The Polyesters Of The Invention

Broadly the polyesters of this invention are 1,4-arylene monomers suchas terephthalic acid and hydroquinone, or a 2,6-arylene monomers such as2,6-dihydroxynaphthalene, which are reacted with a linear and unbranchedaliphatic diacid or diol whose functionality will be reactive with thefunctionality of the arylene monomer. The polyesters of the inventionmay be made by condensation of a diacid with diol by transesterificationsuch as transesterification of hydroquinone diacetate or 2,6-naphthalenediacetate with an aliphatic diacid. The polyesters of the inventiongenerally are made by the transesterification of a dialkyl terephthalatewith straight chain, saturated aliphatic diols; the transesterificationof hydroquinone diacetate with straight chain, saturated aliphaticdiacids, direct esterification with straight chain saturated aliphaticdiacids, esterification of terephalyol chloride with straight chain,unbranched saturated diols, transesterification of 2,6-naphthalenediacetate with straight chain saturated unbranched diols andesterification using dicyclohexyl carbodiimide (DCC), diacid and diol aspreviously described. The alkyl is a lower alkyl having four or lesscarbons. In the latter reactions, any acid halide may be used in lieu ofan acid chloride and propionate or butyrate (lower alkyls having four orless carbons) may be used in lieu of acetate. In this aspect of theinvention, the polyesters may be defined as the reaction product of thea polymeric vehicle wherein the polyester is the reaction product of anarylene monomer selected from the group consisting of ##STR22## andmixtures thereof and a straight chain saturated aliphatic diol or diacidhaving 6 to 17 carbon atoms which diol or diacid is reactive with thearylene monomer and wherein R=alkyl having 1 to 4 carbon atoms or H,R'=alkyl having 1 to 4 carbon atoms and X=halogen.

The polyesters of the invention should generally regularly alternatebetween aromatic substituents and the straight chain unbranchedsubstituents which separate or space the arylene groups. As the spacingbetween arylene groups increases to increase overall molecular weight,the lower number of repeating units enhances the liquid crystalline likeproperties of the polyesters which generally will have a number averagemolecular weight in the range of from about 350 to about 4,000 andpreferably from about 400 to about 1800 corresponding to about m=1 toabout 5 when n=6-10 in Formulas II through V. The degree ofpolymerization or the value of m is controlled by the relativeproportions of monomers in the reaction. For example a 3:2 mole ratio ofmonomer approximately yields a polyester where m=2 for the excessmonomer.

Conversion Of The Polyester Of The General Formula To An Amine Salt.

In converting the polyester to the amine salt according to theinvention, the polyester with a carboxylic acid functionality, or thehydroxyl terminated polyester which has been carboxylated as previouslydescribed, is neutralized with an amine to a pH of about 5.5 to about11, with about 8 to about 8.5 being preferred, to create an amineneutralized polyester which is dispersible in aqueous media. In reactingthe polyester with an amine, the polyester may be dispersed with a smallto moderate amount of organic solvent which is miscible with water(e.g., propoxypropanol or ethanol) and neutralizing amine then beingmixed with the dispersed polyester to form the amine salt of thepolyester. Mixing may be by mild mixing or shearing. Alternatively, anamine, such as a liquid amine may be mixed with the polyester and waterto create a dispersion of the amine salt of the polyester. Cross-linkingagents used with the amine salts of the polyester in an aqueous mediashould be stable in water and will commonly be melamines.

The amines which can be used to make the amine salts in the inventioninclude primary, secondary and tertiary alkyl amines and includetriethyl amine, NHs, N-ethyl morpholine, methylamine, diethylamine,amino-alcohols, such as ethanolamine, diethanolamine, triethanolamine,N-methylethanolamine, N,N-dimethyl-ethanolamine, 3-aminopropanol andtheir ethers, such as 3-methoxypropylamine.

Methods For Providing Anti-Sagging Shear Thinning And ThixotropicProperties.

Important aspects of the invention also include a method for providingpolymeric vehicles with anti-sagging thixotropic and shear thinningproperties and a method of providing polymeric vehicles with theseproperties.

In one aspect, the invention provides a method for increasing theviscosity of a polymeric vehicle which comprises oligomers and issubstantially free of polymers having a number average molecular weightgreater than about 10,000. As used herein, "substantially free ofpolymers" means that the polymeric vehicle prior to curing does not havea number average molecular weight greater than about 2,000 or a weightaverage molecular weight greater than about 6,000. According to thisaspect of the invention, the invention provides a method for increasingthe viscosity of a polymeric vehicle when the polymeric vehicle isheated above temperatures most preferably as low as about 25° C. Thetemperature from which the polymeric vehicle is heated and yet increasesin viscosity during such heating preferably may be as low as about 50°C. and may be as low as about 75° C. Generally the viscosity increasewill be between the latter temperatures and about 100° C. The method forincreasing the viscosity of a polymeric vehicle comprises dispersing thepolyester of general Formula I or amine or oxirane adducts of suchpolyester with a cross-linking agent and a second oligomer to provide adispersion at about 25° C. which provides a polymeric vehicle withantisagging properties. This addition modifies the oligomeric polymericvehicle and provides a modified polymeric vehicle comprising an amountof the composition of the general Formula I or adducts thereof in amounteffective for providing a modified polymeric vehicle which has aviscosity which will increase as it is heated from about 25° C., about50° C. or about 75° C.

Generally to practice the method of this aspect of the invention andprovide novel polymeric vehicles and formulated coating compositionsthat are part of this invention, the polymeric vehicle will comprise atleast about 30 weight percent of the polyester composition of thegeneral Formula I and/or adducts thereof. The novel formulated coatingcomposition will be a dispersion which includes the polyesters ofFormula I and/or the amine salts of such polyesters and/or the oxiraneadducts of such polyesters. The polymeric vehicle will further comprisea cross-linker resin, and may also include other polymeric componentswhich have a number average molecular weight not greater than about10,000 (oligomers). In a very important aspect of the invention, thecross-linker resin and/or other oligomeric components of the polymericvehicle together with the compound of the general formula provide a lowVOC formulated coating composition. Indeed, the formulated coatingcomposition (or polymeric vehicle) may not only be low in VOCs, but maybe solventless, to wit: substantially free of organic solvent which is aVOC and/or water. As a formulated coating composition, the solventlessformulated coating composition includes catalysts, pigments and otheradditives. In this connection substantially free of water and/or organicsolvent means not more than about 5 weight percent of water or VOCsseparately or combined as measured by ASTM test D-1644-59.

The cross-linker agent and the oligomeric components (in addition to thecompound of the general formula or adducts thereof) are reactive witheach other to provide a resulting coating binder having a pencilhardness of at least 3H and a reverse impact resistance of at least 60inch-lbs. at a binder thickness of about 1 mil. In this aspect of theinvention the cross-linking agent includes any di or polyfunctionalsubstance reactive with the polyester of the general Formula I or itsadducts. The cross-linking agent has a number average molecular weightnot greater than about 10,000 such substances including aminoplasts,amines regular and blocked, di and polyisocyanates. Oligomericcomponents which may be used additional to the cross-linking resin, butother than the composition of the general formula include polyestersfrom cyclohexyldiols such as K-Flex 188 and 128 which are available fromKing Industries, Norwalk, Connecticut, K-Flex 128 being the lowermolecular weight product. All of the additional oligomeric componentshave a number average molecular weight of less than about 10,000.

The method of the invention includes dispersing the polyesters ofFormula I and/or the adducts thereof with the cross-linking agent toprovide a low VOC polymeric vehicle which is a dispersion substantiallyfree of polymers having a number average weight of more than about10,000. The polymeric vehicle and a formulated coating composition havea viscosity which increases as the temperature of the polymeric vehicle(or formulated coating) is increased from a selected temperature, about25° C., about 50° C. or about 75° C. This viscosity increase avoidssagging after the polymeric vehicle is applied and heated to cure.

In another aspect the invention also provides a method for increasingthe shear thinning of a low VOC polymeric vehicle which also may be asolventless polymeric vehicle (substantially free of water and/ororganic solvent as previously defined). The method of increasing theshear thinning of a polymeric vehicle comprises dispersing the polymericvehicle with the polyester of the general Formula I or adducts thereof.This method provides a high solids, low VOC modified polymeric vehiclecomprising the polyesters of the general Formula I or adducts thereof inan amount effective for the increase in shear thinning of the polymericvehicle. The method of the invention provides a modified polymericvehicle with a viscosity of not more than about 5 Pa.s at a shear rateof at least about 3,000 sec⁻¹ at temperatures in the range of from about25° C. to about 100° C., preferably not greater than 1.2 Pa.s and mostpreferably not greater than 0.02 Pa.s. Most preferably the shearthinning will be at about 25° C., but preferably at about 50° C. or atabout 75° C. To achieve the shear thinning as provided by the method,the polymeric vehicle will not require more than about 90 weight percentof the polyesters of general Formula I or adducts thereof (with theremaining amount of polymeric vehicle being about 10 weight percentcross-linking agent), but will comprise at least about 40 weight percentof these polyesters or adducts to not only provide the shear thinning asaforesaid, but also to provide a coating binder having a pencil hardnessof at least 3H and a reverse impact resistance of at least 60 inch-lbs.at a binder thickness of 1 mil. In this aspect of the invention,cross-linking resins are any di or polyfunctional substance having anumber average molecular weight not greater than about 10,000 and whichare reactive with the polyesters of general Formula I or adducts thereofas described above. The oligomeric components which may be in additionto the composition of the general formula include K-Flex 128 and 188.

Combining the methods of shear thinning and increasing viscosity atelevated temperatures provides a truly unique polymeric vehicle,especially in the aspects of the invention which provide a low VOCformulated coating composition or a "solventless" coating composition.

Achieving an increase in viscosity at increasing temperatures withoutusing polymers, especially with polymers with heretofore known mesogens,provides the methods and polymeric vehicles of the invention with animportance and uniqueness heretofore not known in the art pertaining tocoating binders for protective paint coatings. Moreover, in view ofenvironmental concerns, this importance is magnified when the inventionprovides low VOC or "solventless" formulated coating compositions.

The polymeric vehicle according to the invention may be used withformulated coatings which are dried at ambient temperature and bakedformulated coatings.

The following examples set forth exemplary methods of making oligomers,polymers and coatings according to the invention.

EXAMPLE I

Transesterification of Hydroquinone diacetate with diacids forpreparation of COOH-terminated oligomers. ##STR23##

Hydroquinone diacetate and a straight chain saturated aliphatic diacid(where n=6, 8 or 10) in a mole ratio of 2:3, zinc acetate dihydrate(0.0065 ppm) and antimony oxide (0.025 ppm) were placed in a three-neckflask equipped with stirrer, thermometer, condenser, and Dean-Stark trapand nitrogen gas inlet. The reactants were heated to 230° C. in a periodof 1 hour and kept at this temperature with stirring for another 2hours. The sample was then dissolved in CH₂ Cl₂, precipitated byethanol, filtered, washed by ethanol and dried in oven at 40° C. for 24hours. Yield was 70-80%. NMR and FT-IR for 7 g: NMR(CDCl₃) 1.35, v.s.(--CH₂ --), 1.75,s.bro.(--CH₂ CH₂ --COO--), 2.4, m(--CH₂ --COOH), 2.6,s. (--CH₂ OOO--C₆ H₄ --), 7.25,s. (benzene). FT-IR, 3000 cm⁻¹,s.bro.(--COOH), 2919 and 2851 cm⁻¹,s, (--CH₂ --), 1747 and 1191 cm⁻¹ s,(--COO--).

EXAMPLE Ia

Direct Esterification of Hydroquinone with Diacid for Preparation OH--or COOH-- Terminated Oligomers (nHQ or CnHQ).

Hydroquinone and saturated aliphatic diacid in a mole ratio of 3:2 (forhydroquinone-terminated) or 2:3 (for COOH-terminated), xylene (about 8%by weight, for azeotrope with H₂ produced), and p-toluenesulfonic acid(p-TSA) (0.2% by weight) are mixed in a three-neck flask equipped withstirrer, thermometer, condenser, Dean-Stark trap, and nitrogen gasinlet. The mixture is heated to 140° C. in a period of 1 hour and keptat this temperature for another 6 hours. The temperature is then raisedto 170° C. and kept there for 4 hours. The sample is recrystallized fromhot toluene, washed with acetone, and vacuum stripped at 80° C. for 18hours. Yields are about 60-85%.

EXAMPLE II

Esterification of 2,6-dihydroxy nahthalene with diacids for preparationof COOH-terminated oligomers. ##STR24##

A mixture of the 2,6-dihydroxynaphthalene, straight chain saturatedaliphatic diacid (where n=8 or 10) in a 2:3 mole ratio, para toluenesulfonic acid (p-TSA) (0.2% wt.) and Aromatic 150 (about 10% wt.) wereheated at 230° C. for 2 hours under N₂ gas in three-neck flask equippedwith stirrer, Dean-Stark trap, condenser, thermometer and N₂ inlet.Distillate was collected in the Dean-Stark trap. The reaction productwas cooled down to 70°-80° C. and dissolved in CH₂ Cl₂ under heating andstirring, the hot solution was poured into ethanol, precipitating thewhite product. Product was filtered, washed with two portions of ethanoland dried at 40° C. overnight. Yield was 60-70%. NMR and FT-IR for 8 g:NMR(CDCl₃) 1.3 s. (--CH₂ --), 1.75 bro(--CH₂ CH₂ --COO--), 2.7 w (CH₂--COOH), 2.8w (--CH₂ COO--C₆ H₄ --), 5-7 multiple (naphthalene); FT-IR3041cm bro. (--COOH); 2926 and 2852 cm⁻¹ s. (--CH₂ --), 1757 and 1215 s.(--COO--), GPC: M_(n) =1.85×10³, M_(w) =3.45×10³ for 8e; M_(n)=1.64×10³, M_(w) =3.94×10³ for 8 g.

EXAMPLE III

Esterification of 2,6-dihydroynaphthalene with diacid usingdicyclohexylcarbodiimide (DCC). ##STR25##

A solution of 2,6-dihydroxynaphthalene (0.05 mole), aliphatic diacid(where n=8 and 10) (0.075 mol), dicyclohexyl carbodiimide (DCC) (0.0733mole), para toluene sulfonic acid (p-TSA) (0.004 mole) and pyridine (150mL) were stirred at room temperature. After stirring 24 hrs. a whitesolid was filtered to remove dicyclohexane urea (DCU). The solution wasconcentrated on a rotary evaporator, the residue was dissolved in CHCl₃and washed with two portions of 10% HCl aq. followed by water until thewater was neutral. The solution was dried over anhydrous MgSO₄ andfiltered. The residue was separated from CHCl₃ with ethanol, followed byfilteration. Residue was dried in an oven at 40° C. overnight. Yield was50-75%. NMR and FT-IR indicate that the products formed by the DCC havesimilar structure as by other methods. As for 10e and 10g, the moleratio is 3:2 of hydroxynaphthalene and diacid.

A. Preparation of water reducible dispersion for 7c, 7e, 7g and 8e, 8gof Examples I and II.

After the above reactions were completed, the products were cooled to160° C. under stirring. Butyl cellosolve and dimethylethanolamine (DMEA)were added to reduce the temperature to 110°-130° C. The pH was adjustedto about 8 and the latter temperature range was maintained for 30 min.Water was added to yield a water reducible dispersion, which was usedwithout purification. Non-volatile weight (NVW) is determined after 2hours of drying at 120° C. (the solid content is about 50%, the solventcontains 80% water).

B. Enamel preparation

The water reducible dispersion of the above samples, HMMM (Resimene 731)and p-TSA in a 70/30/0.3 wt. ratio were cast on steel panels and werebaked at 175° C. for 20 min. The film thicknesses were an average of0.004 in. (4 mil).

C. Results and discussion

DSC:DSC thermograms for 7c, 7e, 7g and Be, 8g, 10e, 10g generally showedtwo or more transitions on heating and cooling, however, 9e and 9gexhibit single peak on heating. The transition temperature of thesesamples are listed in Table 1. However, the same polymers synthesized bydifferent methods (such as DCC, direct transesterification) haddifferent transition temperatures in DSC. Differences are possibly dueto different molecular weight, as an increase of the oligomer molecularweight increases phase transition temperatures.

WAXS:Diagrams exhibit three peaks obtained from sample quenched from 5°C. above T_(m). For example, the d-spacing of 16.3Å in 8e indicates alayered structure; the d-spacing at 4.08 and 4.35Å in 8e areattributable to lateral distances between rigid molecules in the layers.These data are listed in Table 2.

Experimental results indicate that these polymers appear to have liquidcrystalline properties. Soft methylene spacers have been found toenhance liquid crystallinity in many cases. Because flexible linkinggroups can exist in multiple conformations, they tend to enableformation of liquid crystals under suitable circumstances.

D. Physical properties.

The coatings of water reducible dispersion made from the above polymershave good mechanical properties, as listed in Table 3.

                  TABLE 1                                                         ______________________________________                                        Thermal properties of oligomers for 7c,                                       7e, 7g, 8e, and 9c, 9g, 10e, 10g.                                                     Heating         Cooling                                               No.     n     T.sub.1  T.sub.2                                                                            T.sub.3 T.sub.1                                                                            T.sub.2                              ______________________________________                                        7c      6     202.3    220.4                                                                              232.8   194.7                                                                              220.4                                7e      8     133.5         158.6   148.3                                                                              119.2                                7g      10    131.8         148.4   137.3                                                                              119.9                                8e      8     138.4    145.3                                                                              157.1   153.4                                                                              125.9                                8g      10    130.7         145.6   138.2                                                                              122.6                                9e      8     133.8                 138.9                                                                              124.1                                9g      10    113.9                 112.7                                                                              102.8                                10e     8     115.0    128.0                                                                              143.5   143.1                                                                              104.1                                10g     10    113.9    155.1                                                                              164.9   158.4                                                                              146.4                                ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        The peaks of WAXS for 7c, 7e, 7g, and 8e, 8g.                                 No.       n     d - spacings (Å)                                          ______________________________________                                        7c        6     10.85        4.98 4.14                                        7e        8     14.14        4.28 4.02                                        7g        10    17.03        4.40 4.09                                        8e        8     16.25        4.35 4.08                                        8g        10    17.24        4.29 4.03                                        ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        The mechanical properties of films made from                                  the water reducible dispersion of 7c, 7e, 7g and 8e, 8g.                      Tukon              Impact resistance                                          hardness           (Lb-In)                                                    No.     (KHN)          Direct  Reverse                                        ______________________________________                                        7c      22             160     60                                             7e      28             160     120                                            7g      27             160     60                                             8e      27             160     160                                            8g      18             160     160                                            ______________________________________                                    

EXAMPLE IV

Diol/Terephthalic Acid Polyesters

Carboxylyic acid functional polyesters were prepared from terephthalicacid (TPA) and linear aliphatic diols as shown below: ##STR26## whereinn=2, 6 and 10 for the diol.

The properties of polyesters (A):

Appearance: milky white solids.

lo Differential Scanning Calorimetry (DSC): Two transitions for n=6, 10(113.0° and 121.8° C. for n=6; 89.7° and 105.3° C. for n=10); capillaryobservation indicates solid-liquid transition at the lower transitiontemperature.

No transition was observed for n=2 up to 350° C. (decompose).

X-ray diffraction: Samples quenched from 5° C. above T_(m) show severalstrong peaks at wide angle region, indicating crystallinity attemperatures above T_(m).

Solubility: Insoluble in ketones, alcohols, esters, etc.; slightlysoluble in chloroform.

EXAMPLE lVa

Modify the polyester A with an epoxy known as Glydexx N-10 availablefrom the Exxon Chemical Company. ##STR27## where R in Clydexx representsaliphatic groups, the three R groups having a total carbon number of 8;TPBPC is triphenyl benzyl phosphonium chloride.

Properties of (IVB):

Appearance: All grafted polyesters (n=2, 6, 10) are milky white to lightyellow non-transparent viscous liquids.

X-ray diffraction: Several sharp peaks in the wide angle region,indicating crystallinity of these liquid samples.

    ______________________________________                                        DSC:  two first order transitions at 23.5 and 60.9° C.                                                for n = 10;                                          two first order transitions at 40.6 and 90.1° C.                                                for n = 6;                                           no well-defined transitions were observed                                                              for n = 2.                                     ______________________________________                                    

Dispersibility: All form stable high solids (60-80%) dispersions inseveral solvents at room temperature.

n=10: 80% solids dispersion in methylisobutylketone and butyl acetate;70% solids in xylene and 2-heptanone.

n=6: 60% solids dispersion in methylisobutylketone, 2-heptanone, butylacetate, and xylene; clears to transparent solution when heated toelevated temperatures below 100° C.

n=2: 80% solids dispersion in 2-heptanone and butyl acetate; becomes twophases when diluted to 60% solids (a clear top phase and a concentrateddispersion).

EXAMPLE IVb

Cross-linking Polyester IVB with hexakis (methoxymethyl) melamine resin(HMMM).

Formulation:

    ______________________________________                                        Polyester (IVB)        1.4 g                                                  HMMM Commercially available                                                                          0.6 g                                                  as Resimene 746                                                               Para-toluenesulfuric acid                                                                            0.004 g (0.2%)                                         (p-TSA)                                                                       xylene                 1.0 g                                                  ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                                    n = 10  n = 6     n = 2                                           ______________________________________                                        Pencil hardness                                                                             4H/5H     6H/7H     7H/8H                                       Tukon hardness (KHN)                                                                          9        18        30                                         Reverse impact resistance                                                                    80       >160      >160                                        (inch-pounds)                                                                 Direct impact resistance                                                                    >160      >160      >160                                        (inch-pounds)                                                                 Appearance    glossy,   glossy,   some fuzzy-                                               no defects                                                                              pinholing looking                                     ______________________________________                                    

Film thickness about 1 mil; same thickness for other films.

X-ray: For n=6, some weak peaks in the wide angle region, indicatingsome crystal domains; for n=2, several sharp peaks in the wide angleregion, indicating high crystallinity.

EXAMPLE IVc

Cross-linking Polyester IVB with a toluene-diisocyanate prepolymer(Mondur CB-60)

Formulation (as for n=10):

    ______________________________________                                        Polyester (IVB)   1.27 g (0.0020 equivalents)                                 Mondur CB-60*     0.89 g (0.0022 equivalents)                                 dibtutyltine dilaurate                                                                          0.0043 g (0.2% w/w)                                         xylene            1.0                                                         ______________________________________                                    

Baking condition: 70° C. for 30 minutes.

Film properties:

    ______________________________________                                                    n = 10  n = 6     n = 2                                           ______________________________________                                        Pencil hardness                                                                             HB/H      3H/4H     6H/7H                                       Tukon hardness (KHN)                                                                         10        18        30                                         Reverse impact resistance                                                                    80       >160      >160                                        (inch-pounds)                                                                 Direct impact resistance                                                                    >160      >160      >160                                        (inch-pounds)                                                                 Appearance    glossy,   glossy,   some fuzzy-                                               no defects                                                                              pinholing looking                                     ______________________________________                                    

X-ray: For n=6, some weak peaks in the wide angle region, indicatingsome crystal domains; for n=2, several very strong sharp peaks in thewide angle region, indicating high crystallinity.

* Mondur CB-60 is an adduct of toluene diisocyanate and a triol.

EXAMPLE V

Terephthalic acid (TPA)/diol/Polyesters.

Hydroxy functional polyesters were prepared from TPA and diols by themethods shown below. ##STR28## wherein n=6, 7, 8, 9, 10, 12 or 16

where DCC represents dicyclohexylcarbodiimide and DCU representsdicyclohexylurea.

Properties of Polyesters (VC):

DSC: Two or three first order transitions on heating and one or moretransitions on cooling, typical of LC polymers.

Cross-polarizing microscope: The samples quenched from 5° C. above T_(m)shows batonnet or grain-like textures, indicating possible smectic C ornematic structure.

X-ray: Several peaks in the wide angle region and a medium peak in thesmall angle region, indicating possible smectic C structure.

Solubility: Soluble in chloroform and dichloromethane; insoluble inketones, alcohols, esters, etc.

Esterification Using DCC for Preparation of Polyesters of the Type nGT,nHO, CnHQ, and CnGT where nGT means --OH terminated polyester, CnGTmeans --COOH Terminated Polyester, nHQ means --OH Terminated Polyestermade with Hydroquinone and CnHQ means a --COOH Polyester made withHydroquinone.

Terephthalic acid (or saturated aliphatic diacid) (0.02 or 0.03 mol),saturated aliphatic diol (or hydroquinone) (0.02 of 0.03 mol), p-TSA(0.0024 mol), and DCC (0.044) is dissolved in 200 ml of pyridine in asingle-neck flask with DCC being added last. A white precipitate beginsto appear in about 2-10 min., which is dicyclohexylurea (DCU). Afterstirring at room temperature or elevated temperature (up to 80° C.) for24 to 6 hours, the reaction solution is filtered to remove DCU,concentrated on a rotary evaporator, and dissolved in CH₂ Cl₂ to removethe remaining DCU. The CH₂ Cl₂ solution is washed with 3 portions of 10%HCl and 3 portions of water, dried over MgSO₄, and concentrated to ahigh concentration (polyester not precipitated yet). The polyester isprecipitated by adding acetone. The sample is dried over vacuum at 60°C. for 8 hours. Yields are about 50-90%.

EXAMPLE Va

Modify Polyester VC with succinic anhydride and then with Glydexx N-10.##STR29##

Properties of the Glydexx N-10 grafted polyester (n=10):

Appearance: Milky white to light yellow non-transparent viscous liquid,indicating crystallinity or liquid crystallinity in the liquid sample.

DSC: For n=10, two transitions (28.7° and 69.8° C.) are observed,typical of LC polymers.

Polarizing microscope of quenched sample: grain- and batonnet-liketextures, indicating possible nematic or smectic C structures.

X-ray: Several strong peaks in the wide angle region and a medium peakat small angles (6.24°, 14.14 Å), suggesting possible smectic C orcybotactic nematic (nematic with short-range smectic-like ordering)structure.

Solubility: Form stable dispersion in toluene and MIBK (methyl isobutylketone) with 60-80% solids.

EXAMPLE Vb

Cross-linking of non-grafted polyester (VC) wherein n=10 with HMMM.

Formulation:

    ______________________________________                                        Polyester (VC)  1.4 g                                                         HMMM (Resimene 746)                                                                           0.6 g                                                         p-TSA           0.004 g                                                       toluene         3.0 g (soluble only at elevated temp.)                        ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                        Pencil hardness       6H/7H                                                   Tukon hardness         20 KHN                                                 Reverse impact resistance                                                                           >160 inch-lbs.                                          Direct impact resistance                                                                            >160 inch-lbs.                                          Appearance            fuzzy-looking                                           ______________________________________                                    

EXAMPLE Vc

Cross-linking of Glydexx N-10 grafted polyester (VD) with HMMM (Resimene746).

Formulation:

    ______________________________________                                        Polyester (VD)          1.4 g                                                 HMMM (Resimene 746)     0.6 g                                                 p-TSA                   0.004 g                                               toluene                 1.0 g                                                 ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                        Pencil hardness       3H/4H                                                   Tukon hardness         20 KHN                                                 Reverse impact resistance                                                                            60 inch-lbs.                                           Direct impact resistance                                                                            >160 inch-lbs.                                          Appearance            glossy- no defects                                      ______________________________________                                    

EXAMPLE VI

Terephthalic acid/diol/Phthalic Anhydride/Glydexx N-10 modifiedoligomer.

Polyester (VC) (containing a repeating unit of 2 as the cases before)was grafted or reacted with phthalic anhydride (PA) and then withGlydexx N-10. ##STR30## wherein n=6, 10 and 12.

The properties of the Glydexx N-10 grafted oligoester (with n=10):

Appearance: Milky white to light yellow non-transparent viscous liquid.

X-ray: Several peaks in the wide angle region and a weak peak in smallangles (6.06Å, 14.6 Å).

Solubility: Form stable dispersion in toluene with 60% solids.

EXAMPLE VIa

Cross-linking oligomer VIE with HMMM (Resimene 746).

Formulation:

    ______________________________________                                        Oligoester (IVE)        1.4 g                                                 HMMM (Resimene 746)     0.6 g                                                 p-TSA                   0.004 g                                               toluene                 2.0 g                                                 ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                        Pencil hardness       3H/4H                                                   Tukon hardness         12 KHN                                                 Reverse impact resistance                                                                            >80 inch-lbs.                                          Direct impact resistance                                                                            >160 inch-lbs.                                          Appearance            glossy- no defects                                      ______________________________________                                    

EXAMPLE VlIa

Terephthalic Acid/diol/Trimellitic Anhydride Oligoesters.

The oligoester (VC) (containing 2 repeating units) was grafted orreacted with trimellitic anhydride (TMA) and then was grafted or reactedwith Glydexx N-10 as shown below. ##STR31## wherein n=6, 10 and 12.

The properties of the Glydexx N-10 grafted oligoester (with n=10):

Appearance: Light yellow transparent semisolid.

X-ray: Several peaks in the wide angle region and a weak peak in thesmall angle region (6.6°, 14.6Å) indicating LC structure of thematerial.

Solubility: Form dispersions in toluene with 60-80% solids.

EXAMPLE VIIb

Cross-link oligomer VIIF with HMMM (Resimene 746).

Formulation (n=10):

    ______________________________________                                        Oligoester (VIIF)       1.4 g                                                 HMMM (Resimene 746)     0.6 g                                                 p-TSA                   0.004 g                                               toluene                 1.0 g                                                 ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                        Pencil hardness       6H/7H                                                   Tukon hardness         15 KHN                                                 Reverse impact resistance                                                                            >80 inch-lbs.                                          Direct impact resistance                                                                            >160 inch-lbs.                                          Appearance            glossy- no defects                                      ______________________________________                                    

EXAMPLE VlIc

Cross-link oligoester (VIIF) with a toluenediisocyanate prepolymer.

Formulation (n=10):

    ______________________________________                                        Oligoester (VIIF) 1.02 g (0.0030 equivalents)                                 Mondur CB-60      1.33 g (0.0033 equivalents)                                 dibutyltin dilalurate                                                                           0.005 g (0.2% w/w)                                          toluene           1.0 g                                                       ______________________________________                                    

Baking condition: 70° C. for 30 minutes.

Film properties:

    ______________________________________                                        Film Properties:                                                              ______________________________________                                        Pencil hardness       6H/7H                                                   Tukon hardness        22 KHN                                                  Reverse impact resistance                                                                           >160 inch-lbs.                                          Direct impact resistance                                                                            >160 inch-lbs.                                          Appearance            glossy, no                                                                    defects                                                 ______________________________________                                    

EXAMPLE VIII

Terephthalic acid/diol/epoxy modified polyesters.

Glydexx N-10 was directly grafted onto Oligoester (C) as shown below.##STR32##

Properties:

Appearance: Light yellow, turbid, viscous liquid (for n=10, 6), typicalof LC polymers.

DSC: For n=10, three transitions: 10.3°, 47.0° and 64.0° C.

Cross-polarizing microscope: Grain-like structure.

Solubility: For n=10, 30% clear solution in toluene; 70% stabledispersion in toluene.

EXAMPLE VIIIa

Polyester VIIIG cross-linked with HMMM (Resimene 746).

Formulation:

    ______________________________________                                        Polyester (VIIIG)       1.4 g                                                 HMMM (Resimene 746)     0.6 g                                                 p-TSA                   0.004 g                                               toluene                 1.0 g                                                 ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                                         Polyester                                                                              (VIIIG)                                                              n = 6    n = 10                                              ______________________________________                                        Pencil hardness    6H/7H      6H/7H                                           Tukon hardness (KHN)                                                                              25         20                                             Reverse impact resistance                                                                         80         160                                            (inch-pounds)                                                                 Direct impact resistance                                                                         >160       >160                                            (inch-pounds)                                                                 Appearance         glossy,    glossy,                                                            no defects no defects                                      ______________________________________                                    

Film thickness about 1 mil; same thickness for other films.

X-ray of Resimene 746 cross-linked film (n=10): a broad refraction peakin the wide angle region and a weak but sharp peak in small angles(4.93°, 17.9 A), indicating that the film is generally in an amorphousstate but also contains some liquid crystal domains.

EXAMPLE IX

Hydroquinone/Diacid/Polyesters.

Carboxylic acid functional polyester from hydroquinone (HQ) and linearaliphatic diacids were prepared as shown below. ##STR33## wherein n=10.

Properties of the polyester with n=10:

Appearance: Light brown solid.

DSC: Three first order transitions on heating (100.4°, 115.0°, and129.8° C.) and three on cooling (93.4°, 105.1°, and 124.1° C.),indicating liquid crystal behavior.

X-ray: Two sharp peaks in the wide angle region and one sharp peak insmall angles, indicating smectic structure.

EXAMPLE lXa

Polymer IXH was grafted with Glydexx N-10 as shown below. ##STR34##

The material with n=10 is a yellow brown viscous liquid.

EXAMPLE IXb

Polymer IXI was cross-linked with HMMM (Resimene 746).

Formulation (n=10):

    ______________________________________                                        Polyester (IXI)         1.4 g                                                 HMMM (Resimene 746)     0.6 g                                                 p-TSA                   0.004 g                                               toluene                 2.0 g                                                 ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                        Pencil hardness        3H/4H                                                  Tukon hardness          13 KHN                                                Reverse impact resistance                                                                             80 inch-lbs.                                          Direct impact resistance                                                                             160 inch-lbs.                                          ______________________________________                                    

EXAMPLE X

Diacid/Hydroquinone/Epoxy Modified Polymers

Hydroxy functional polyesters were prepared from hydroquinone (HQ) andlinear saturated aliphatic diacids as shown below. ##STR35## whereinn=4, 6 and 10.

Properties of the polyester with n=10:

Appearance: Light brown solids.

DSC: Three first order transitions on heating (85.0°, 104.7°, and 120.8°C.) and three on cooling (61.7°, 85.6°, and 103.8° C.), indicatingmultimesomorphous liquid crystal behavior.

Crossed polarizing microscope: Brush- and grain-like (quenched from 80°C.) and schlieren (quenched from 100° C.) textures, indicating possiblesmectic C and B structures.

X-ray: Three strong sharp peaks in the wide angle region and two mediumsharp peaks in small angels, indicating smectic structures.

EXAMPLE Xa

Polyester X was grafted with Glydexx N-10 as shown below. ##STR36##

The material with n=10 is a yellow brown viscous liquid.

EXAMPLE Xb

Polyester XK was cross-linked with HMMM (Resimene 746).

Formulation (n=10):

    ______________________________________                                        Polyester (XK)          1.4 g                                                 HMMM (Resimene 746)     0.6 g                                                 p-TSA                   0.004 g                                               toluene                 2.0 g                                                 ______________________________________                                    

Baking condition: 150° C. for 30 minutes.

Film properties:

    ______________________________________                                        Pencil hardness        3H/4H                                                  Tukon hardness          13 KHN                                                Reverse impact resistance                                                                             80 inch-lbs.                                          Direct impact resistance                                                                             160 inch-lbs.                                          ______________________________________                                    

EXAMPLE XI

Synthesis of ##STR37##

A mixture of HOOC--(CH₂)₁₀ --COOH, p-hydroxybenzoic acid (PHBA),methansulfonic acid (MSA) and Aromatic 150 (a mixed alkyl benzenesolvent commercially available from Exxon Chemical Company) are heatedunder N₂ in a 3-neck flask equipped with stirrer, Dean-Stark trap,condenser and thermometer. The PHBA/diacid mole ratio is 1/2 and 0.1 wt.% of methanesulfonic acid is used. The amount of Aromatic 150 isadjusted to maintain the temperature at 220°-230° C.; about 10 wt.% isneeded. Distillate (cloudy H₂), usually 95-99% of theoretical amount, iscollected in the Dean-Stark trap during 5-7 hr. The reaction mass arecooled to 115° C., and methylisobutylketone (MIBK) are added for easyhandling. The reaction mass are directly poured out from flask into asample can at about 200° C.

The crude product is dried in oven at 120° C. and cooled and ground. Theproduct is washed 3-4 times with methanol and centrifuged if necessary.Then oven drying and grounding is applied repeatedly. The purifiedproduct is dried overnight in oven at 110° C. The yield varies, but isabout 10% or higher.

EXAMPLE XII

Synthesis of poly hexanediol terephthalate. ##STR38##

Two moles acid chloride of terephthalic acid ##STR39## and three molesof 1,6-hexanediol HO (CH₂)₆ OH! are placed in a 100 mL flask equippedwith a distillation extender, a septum, and a stirring magnet. The flaskis flushed with argon for 15 min. then heated in an oil bath at about150° C. The HCl in the argon flow can be monitored by pH paper--a morequantitative method uses a basic solution of known normality and allowsthe argon flow to bubble through. The solution is then titrated and theextent of reaction can be calculated. The reaction time is about 4 to 8hours.

EXAMPLE XIII

Non-Aqueous Dispersion Of Modified Polyester And Blends Of Polyester OfGeneral Formula And Modified Polyester.

XIII(a)--Polyester Having LC-like Properties

The diol polyester having the formula ##STR40## was made as follows.

59.1 g (0.50 mol) 1,6-hexanediol, 58.3 g (0.30 mol) dimethylterephthalate ##STR41## and 0.235 g (0.2% w/w) zinc acetate dihydrate(ZnAc.2H₂ O) were charged to a 250-mL flask equipped with thermometer,stirrer, nitrogen gas inlet, and Dean-Stark trap. The mixture was heatedto 200°-220° C. in about one hour and kept at this temperature rangewith stirring until no more condensed liquid came out (in about 1 to 2hours). The material was dissolved in hot acetone, recrystallized,filtered, and dried at 70° C. in an oven for 5 hours. 75 g white solidwas collected (yield: 76.0%); NMR indicates the expected molecularstructure and a repeating unit of x=2.0. As a by-product, 15 g lowermolecular weight (n<2.0) polyester was collected after evaporating thefiltered acetone.

EXAMPLE XIII(b)

Modified Polyester Having LC-Like Properties

The polyester (XIIIa) was modified with the mono-oxirane Glydexx N-10 bycarboxylating the polyester and reacting the carboxylated polyester withthe as follows. ##STR42##

61.5 g (0.1 mol) XIIIa and 38.4 g (0.2 mol) trimellitic anhydride werecharged into a 250-mL flask equipped with stirrer, thermometer, watercondenser, and nitrogen gas inlet. The mixture was heated to 180° C. inone hour and kept at this temperature for another hour. 100.0 g (0.40mol) Glydexx N-10 and 0.20 g triphenyl benzyl phosphonium chloride(TPBPC, 0.20 g/mol epoxide) were added. The mixture was heated at150°-180° C. for 90 minutes. The sample was diluted with 150 g toluene,poured into a 800-mL beaker, and washed with 3 portions of 400 mLpetroleum ether with the supernatant liquid being recanted each time.The washed sample was then dissolved in 300 mL toluene and theprecipitate (if any) was filtered out. The solution was concentrated ona rotavap and then heated to 150° C. to remove all the solvents. Thefinal product (XIIIb) was light-yellow transparent liquid at highertemperatures and non-transparent semi-solid at room temperature. Yieldwas 162.0 g (81%). The expected structure, as shown above, was verifiedby NMR spectroscopy.

EXAMPLE XIII(c)

Comparative Polyester Without LC-Like Properties

A diol polyester without LC-like properties was made as shown below.That polyester was carboxylated and then modified with the oxiraneGlydexx N-10 as shown below to provide the oxirane modified polyesterXIIIc.

Synthesis of oxirane modified XIIIc ##STR43##

29.62 g (0.20 mol) phthalic anhydride and 35.45 g (0.30 mol)1,6-hexanediol were charged into a 250 mL flask equipped with nitrogengas inlet, thermometer, Dean-Stark trap, and condenser. The mixture washeated to 150° C. in 30 minutes and kept at 150° C. for another 30minutes. 0.13 g ZnAc.H₂ O (0.20% w/w of monomers) was added and thetemperature was raised to 200°-230° C. and kept at this temperaturerange until no more condensed liquid came out (in about 1 hours; 2.8 gwater was collected). 38.4 g (0.2 mol) trimellitic anhydride was addedand the mixture was heated at 150°-180° C. for 1 hour. 100.0 g (0.40mol) Glydexx N-10 and 0.20 g TPBPC (0.20 g/mol epoxide) were added andthe mixture was heated at 150°-180° C. for an additional hour. Thesample was diluted with 150 g toluene and poured into a 800 mL beaker,and washed with 3 portions of 400 mL petroleum ether with thesupernatant liquid being decanted each time. The washed sample wasdissolved in 300 mL toluene and the precipitate (if any) was filteredout. The solution was concentrated on a rotavap and then heated to 150°C. to remove all the solvents. The final product was light-yellowtransparent liquid at room temperature. Yield was 182.0 g (91%). Theexpected structure of XIIIc was identified by NMR spectrum.

PROPERTIES OF DISPERSIONS OF POLYMERS XIII a b & c Dispersion orSolution Preparation

(A) Formation of Dispersions of XIIIa and XIII b ##STR44##

1.9 g of the modified polyester XIIIb and 0.10 g of the polyester XIIIawere charged into a glass vial (uncovered) and heated on a Bunsen burneruntil the polyester XIIIa completely melted. 1.33 g xylene was addedslowly, forming a homogeneous solution. The solution was cooled at roomtemperature with good shaking (or with ultrasonication), untildispersion formed.

(B) XIIIb Only ##STR45##

2.0 g of the polyester XIIIb and 1.33 g xylene were charged into a glassvial and heated on a steam bath until the polyester XIIIb was completelydissolved. The solution was well shaken while cooling at roomtemperature. A dispersion was gradually formed during cooling, whilesome of the polyester XIIIa precipitated on the bottom. However, thesolution became a homogeneous turbid solution (or dispersion) after 24hours.

Instrumental Methods Used In Testing Described In Example XIII

¹ H-NMR spectra were measured at 34° C. at a Varian Associates EM 390NMR spectrometer with tetramethyl silicone (TMS) as internal standard.

Viscosity was measured by an ICI cone and plate viscometer. The samplewas measured 1 day after preparation. The shear rate was about 10,000s⁻¹. For shear thinning sample, the steady state viscosity was recorded.

Differential scanning calorimetry (DSC) was carried out using a Du Pont990 thermal analyzer at a heating rate of 10° C./minute and a coolingrate of 2° C./minute. The lower cooling rate and higher heating ratewere limited by the instrument. Since a specific cooling system was notavailable, cooling was accomplished by the atmosphere. The heating fromvery low temperature (precooled by dry ice) could not be too slow. Thesamples were prepared by drying the dispersions at 100° C. for 30minutes and cooling to room temperature by sitting in the atmosphere.During DSC experiments, samples were contained in sealed aluminum pansand an identical empty pan was used as a reference.

Liquid crystal textures and particle distribution of the dispersionswere examined at room temperature by an Olympus model BH-2 microscopeequipped with crossed polarizers. The liquid samples (as dispersions)were directly examined for particle distribution without evaporation.

Film Casting/Baking And Testing For Example XIII

The coatings were cast film on 1000 Bonderite polished steel panels witha drawdown bar. The coatings were baked at 150° C. for 20 minutes.

After baking the films were tested 1 day after cross-linking. Reverseimpact resistance, Knoop hardness (KHN), acetone resistance, andcrosshatch adhesion were measured according to ASTM D2794, D1474, D2792,and D3359 respectively.

Stability Of The Dispersions Of Example XIII

When hot solutions of mixed polyester XIIIb and polyester XIIIa inxylene were cooled down to room temperature with good shaking, turbiddispersions were formed; no precipitates other than dispersed particleswere observed. Most of the dispersions prepared were stable for at least1 day. After several days, some dispersions were still stable, but someseparated into two layers (phase separation), the one on the top withlower concentration and the other on the bottom with higherconcentration. However, after good shaking or stirring, thephase-separated samples became homogeneous dispersions again. Table 4 inthis Example shows the stability of the dispersions after one week ofpreparation. With the increase in the insoluble polyester XIIIa content,the dispersion became less stable, possibly because less amount ofsoluble polyester will be available to stabilize the insolublepolyesters, causing poorer stability. Stability also increased with thepolymer concentration (or percent solids), possibly because of thehigher viscosity of the liquid phase at higher polyester concentration.

                                      TABLE 4                                     __________________________________________________________________________    Stability of blend of XIIIa and XIIIb in xylene                               dispersions after 1 week.                                                     __________________________________________________________________________    XIIIa in polymer                                                                      2.5%                                                                             5% 7.5%                                                                             10%                                                                              12.5%                                                                             15%                                                                              20%                                                                              30%                                                                              40%                                                                              50%                                       blend                                                                         50% polymer                                                                           SD SD PS PS PS  PS PS PS PS PS                                        blend-in                                                                      dispersion                                                                    60% polymer                                                                           SD SD SD PS PS  PS PS SS SS SS                                        blend-in                                                                      dispersion                                                                    70% polymer                                                                           SD SD SD SD SD  SD SD SS SS SS                                        blend-in                                                                      dispersion                                                                    __________________________________________________________________________     where SD = stable dispersion; PS = phase separation; SS = semisolids.    

The mechanisms for the stabilization of the dispersions are not clear.However, dispersion stabilization is possibly due to the steric effectcaused by the bulky alkyl groups on polyester XIIIb. Some polyesterXIIIb molecules will co-crystallize with polyester XIIIa during thedispersion formation (as will be discussed later). Many of them will beon the particle surface, with the LC segment associated with theparticles and the alkyl groups "dissolved" in the liquid phase, causingentropic (or steric) stabilization.

For a comparison study, non-liquid crystalline polyester XIIIc was usedto replace XIIIb to prepare dispersion. When a hot solution of polyesterXIIIc and polyester XIIIa (XIIIc:XIIIa=9.1) in xylene was cooled downwith shaking, solid species precipitated out. No homogeneous dispersion,as for XIIIb and XIIIa in xylene system, was obtained. Thecrystallization of the insoluble polyester in a transitional non-aqueousdispersion caused flocculation, possibly because the dispersant (solublepolymer) could not co-crystallize with the insoluble polyesters and wasexcluded from the crystal. Such results suggest that in order to formstable dispersion in the current system, the soluble polyester shouldhave a segment with similar (LC) structure to the insoluble polyester.This common structure provides the sites for association between thesoluble and insoluble polyesters, possibly through LC association.

Viscosity vs. Content of Polyester XIIIa In The Dispersions

Viscosity of the dispersions varies with the content of the polyesterXIIIa in dispersions of the blends of polyesters XIIIa and XIIIb. Inthree different concentrations of the blend (50, 60 and 70%), theincrease of XIIIa content caused the viscosity to decrease to a minimumand then increase again. Since polyester XIIIa is insoluble in xylene,it must stay as dispersion (in solid particles), possibly stabilized bysoluble oligomer molecules. Apparently, the viscosity change isaccompanied by the formation of dispersions (solid phase) and thedecreasing solution concentration (liquid phase). While not intending tobe bound by any theory, this can be explained as follows.

For the same percent solids, with the increase of insoluble polyesterXIIIa content, the soluble polyester XIIIb is reduced. Thus, the liquidphase concentration is diluted. If the solid phase (dispersion) were notexisting, the solution viscosity would decrease. However, the solidphase (dispersion) also contributes to the viscosity, causing higherviscosity than the liquid phase alone. Therefore, the viscosity changeis the net result of both the decrease due to the decreasing liquidconcentration and the increase due to the increasing solid phase(dispersion).

It is known that the viscosity of polymer solutions usually increasesslowly at lower concentration but increases dramatically at higherconcentration. This is also true in dispersions of XIIIb. Experimentsdemonstrate that at high concentration (50-70%), with 10% concentrationincrease, the viscosity increases 260%. Thus, at higher concentration, asmall reduction in the concentration would reduce the viscosity greatly.On the other hand, for a solid dispersion in liquid at lowerconcentration (0.30%), the viscosity varies with the solid volumefraction (V) according to the V and equation (an extension of theEinstein equation): ##EQU1## According to this equation, for adispersion at lower concentration (0-30%), the viscosity only increasesmoderately with the concentration. For example, when the dispersionconcentration increases from 0% to 10%, the viscosity increases 32%(2.5×0.1+7.35×0.1); and when the concentration increases from 10% to20%, the viscosity increases 47%. Such a viscosity increase is much lessthan the increase for a polymer solution at higher concentrations (260%increase in viscosity with 10% concentration increase (from 60% to70%)). Thus, for the same percent solids at higher polymerconcentration, with the increase in the solid phase (dispersion) to acertain extent, the viscosity should decrease.

The solid phase may be higher than expected when only considering theinsoluble polymer, since some soluble polyester XIIIb may co-crystallizewith polyester XIIIa and involve in the solid (dispersion) phase. Thus,the viscosity reduction may be different from prediction of the V andequation.

The viscosity of the dispersions of blends of polyesters XIIIa and XIIIbincreased again when the insoluble polyester content (relative to thetotal polyester) exceeded 10-20%. This is possibly because at higherdispersion concentrations the particles are too crowded to move freely,causing higher viscosity.

Liquid Crystallinity of Polyesters XXIXa and XlIIb

The DSC thermogram of polyester XIIIa showed three first-ordertransitions on heating and three first-order transitions on cooling,indicating its multimesomorphous property. The lower-temperaturemesophase is possibly smectic and the higher-temperature mesophase ispossibly nematic. The different intensity ratios among the three peakson heating from those on cooling can be explained in terms of thedifferent relaxation rates of the transitions on heating from those oncooling. The three transitions on heating are about the same possiblybecause all the three relaxation rates on heating are fast enough to bewell observed at the experimental heating rate (assume the threetransition energies are about the same); while on cooling the two lowertransitions are much weaker than the higher-temperature transitionspossibly because the relaxation rates of the two lower-temperaturetransitions are too low to be observed fully at this experimentalcooling rate. This difference in the transition intensity ratios onheating from on cooling also indicates the good purity of thepolyesters, since if each transition were due to different polyesters(varying in structure or molecular weight) there should be no differencebetween the transition ratios on heating and on cooling.

Polyester XIIIb was non-transparent semi-solid or viscous liquid at roomtemperature and transparent liquid at elevated temperatures (above50°-60° C.). The non-transparency at room temperature is possibly due tocrystal (possibly LC) formation. The DSC thermogram of polyester XIIIbhas three first-order transitions (2.6°, 43.0° and 59.0° C.) and asecond-order transition (-18.3° C.) on heating, while no transitionswere observed on cooling above 50° C. (below 50° C., DSC can not becarried out on cooling in this instrument). The two transitions at 43.0°and 59.0° C. are possible due to the phase transitions of the LC units,since the LC unit is the only part in the XIIIb molecule with such hightransition temperatures (the melting/freezing point for pure GlydexxN-10 is less than -20° C.) and these two transition temperatures areclose to the transition temperatures of polyester XIIIa. Also, thesetransition temperatures are in the same range for polyester XIIIb tobecome transparent. Thus these transitions must be crystal or LCtransitions. The somewhat lower transition temperatures of the LC unitsin polyester XIIIb are due to the modification by soft spacers (GlydexxN-10). The clearly separated two transitions due to polyester XIIIaunits in polyester XIIIb indicates its LC behavior, the uppertemperature being clearing point and the lower temperature being meltingpoint. The second-order transition (-18.3° C.) is typical of glasstransition. The first-order transition at 2.6° C. is possibly themelting point due to the non-LC part of the material. This temperatureis higher than the melting/freezing temperature of pure Glydexx N-10(-20° C.) due to the attachment of this molecule onto the high Tm unitswhich makes the Glydexx N-10 unit less mobile, causing higher transitiontemperature.

Morphology of Polyester XIIIc: A Non-LC Oligomer With Structure Similarto Polyester XIIIb

Polyester XIIIc was synthesized as a non-LC oligomer for comparisonstudies of the LC properties of polyester XIIIb. Polyester XIIIc istransparent semi-solid or viscous liquid at room temperature instead ofturbid semi-solid or viscous liquid as for polyester XIIIb, which may bedue to non-crystallinity of XIIIc above room temperature. The DSCthermogram of polyester XIIIc does not have first-order double or tripletransitions from -60° to 150° C., indicating non-liquid crystallinity ofthis polymer. The sharp first-order single transition at 8.2° C. istypical of a melting point, while the weak and broad transition at-17.6° C. is possibly a glass transition. Thus, the two carboxylic acidsbeing in the para positions (as for terephthalate) is important for theformation of LC-like properties; similar polymers with carboxylic acidsin the meta positions will not be liquid crystalline.

Co-Crystallization of Polyester XIIIb with Polyester XIIIa

In order to clarify the possible co-crystallization of polyester XIIIbwith Polyester XIIIa in the dispersions, a DSC is carried out for thedry mixed sample (no solvent) containing polyester XIIIa and polyesterXIIIb with different polyester XIIIa content. A dry sample is used inthe DSC experiment because of the instrumental limitation. However, fromthe dry samples, we can know the co-crystallizability of polyester XIIIawith polyester XIIIb and thus predict the possible co-crystallization inthe dispersions.

DSC thermograms of mix-melted samples of polyesters XIIIa and XIIIb weretaken with different polyester XIIIa content. The DSC plot for purepolyester XIIIa and polyester XIIIb were also compared with DSCthermograms of the blends. Both the transitions due to polyester XIIIa(higher temperature region) and polyester XIIIb (lower temperatureregion) are seen in the thermograms for the mixed samples, indicatingthe existence of two types of LC domains. However, the transitiontemperatures for the domain for polyester XIIIb is higher than for thepure polyester XIIIa and increase with the increasing polyester XIIIacontent; while the transition temperatures for the domain for polyesterXIIIa is lower than for the pure polyester XIIIb and decrease withdecreasing polyester XIIIa content. Also the transition temperatures aregenerally broader than for the pure oligomers. This indicates theinvolvement of the other polyester in either LC domain. That is, apolyester XIIIa LC domain also contains some polyester XIIIb molecules,while a domain for polyester XIIIb also contains some XIIIa polyestermolecules. For the dispersions, the involvement of the XIIIb polyesterin a XIIIa polyester LC domain will lead to the stabilization of thedispersion, since the XIIIb polyester also contains soft alkyl groupswhich will cause steric stabilization of the dispersions.

Crossed Polarizing Microscope Studies of Dispersions of the XIIIa andXIIIb Polyester Blends

Microscope studies have been carried out for blends of XIIIa and XIIIbpolyesters in xylene dispersions with different XIIIa polyester content(10, 20 and 30 weight percent). The dispersions were 50 weight percentpolyesters. Original wet samples were directly used for the studies.Without crossed polarizing lenses, the samples were found to betransparent. Thus polarizing lenses were used for all the samples, andonly the birefrigerant parts of the samples showed up in the microscopeobservation.

Polyester XIIIb in xylene showed a few scattered birefrigerant particlesin the solution or dispersion; while with the addition of polyesterXIIIa, more birefrigerant particles were presented which indicates theinduced LC formation by the XIIIa polyester. The particle size was verysmall at lower XIIIa polyester content; while larger particle size wasobserved when the XIIIa polyester content is high. With higher XIIIapolyester content, the particles are stabilized by less amount ofpolyester XIIIb and have more chance to coalesce with each other; whileat lower polyester XIIIa content the particles are stabilized by morepolyester XIIIb and remain as smaller particles. This also explains thebetter stability of the dispersions with lower polyester XIIIa content.For the dispersions with 10 and 15% polyester XIIIa contents, Brownianmotion indicates these dispersions are deflocculated. This Brownianmotion may also cause stability of the dispersions.

Properties of HMMM-Cross-linked Films Made From Polyesters XIIIa andXIIIb

Table 5 in this Example shows the film properties of the polyesterscross-linked with hexakis (methoxymethyl) melamine resin (HMMM). Nosignificant differences in film properties were observed with differentpolyester XIIIa contents. This indicates that polyester XIIIb gives asgood properties as polyester XIIIa does. Although there are some softgroups on polyester XIIIb, it has 4 functional groups instead of 2 asfor polyester XIIIa. More functional groups will give higher and moreefficient cross-linking, and thus compensate the softness caused by thealkyl groups on polyester XIIIb.

                                      TABLE 5                                     __________________________________________________________________________    Film properties of dispersions of XIIIa and XIIIb                             polyester blends cross-linked with HMMM.*                                     Polyester                                                                     XIIIa in                                                                           Film                                                                              Tukon                                                                             Pen-    Cross-                                                   XIIIa and                                                                          thick-                                                                            hard-                                                                             cil Reverse                                                                           hatch                                                                              Resist-                                             b Blend                                                                            ness                                                                              ness                                                                              Hard-                                                                             Impact                                                                            Adhesion                                                                           ance to                                             (wt. %)                                                                            (mil)                                                                             (KHN)                                                                             ness                                                                              (in. lb.)                                                                         (%)  Acetone                                                                            Appearance                                     __________________________________________________________________________    0    1.4 11  3H/4H                                                                             160 100  Excellent                                                                          Transparent                                    10   1.5 12  3H/4H                                                                             152 100  Excellent                                                                          Transparent                                    20   1.4 11  3H/4H                                                                             160 100  Excellent                                                                          Transparent                                    30   1.4 12  3H/4H                                                                             160 100  Excellent                                                                          Transparent                                    40   1.4 12  3H/4H                                                                             160 100  Excellent                                                                          Transparent                                    __________________________________________________________________________     *Coating composition: oligoesters:HMMM:pTSA = 70:30:0.30 (w/w); solids %      70% (wt. % in xylene); baking schedule: 150° C. for 20 minutes.   

All the films are transparent and very glossy. Because these LColigomers have lower melting and clearing points than the curingtemperature, they were cured from isotropic state. The cross-linkedfilms may remain isotropic or have smaller LC domains (smaller thanlight wavelength). Such a film appearance is very desirable in coatings.

All the films showed good hardness and excellent flexibility. However,the Tukon hardness of these films was not as high as for other LCcoatings, possibly because the LC domains did not form aftercross-linking.

Stable non-aqueous dispersions can be formed from blends of a polyesterof the general formula and a modified polyester. LC association betweenthe soluble and insoluble polymers and the steric effect of the solublepolymer may be the causes of the dispersion stabilization.

At the same polyester blend concentration, the insoluble LC polyesterinduced dispersions showed lower viscosity than the pure solublepolyester solution. The viscosity showed a minimum when the insolublepolyester content is 10-20% of the total polyester content. Thisrheological behavior can be explained in terms of Vand equation togetherwith the fact that the viscosity of polyester solutions at highconcentrations increases significantly with the concentration increase.This viscosity reduction is important for making higher solids coatings.

M-cured films of the dispersions of the polyester/modified polyesterblend showed good mechanical properties and excellent appearance(transparent). This shows that the dispersion formation does not affectthe film appearance.

EXAMPLE XIV

(Reactive Diluent+Diol Polyester) XIV(a)--Synthesis of Reactive Diluent

A reactive diluent having the formula ##STR46## wherein R=aliphaticgroup with R₃ having a total of eight carbon atoms, was made as followsas a reaction product of terephthalic acid (TPA) and the mono-oxirane,Glydexx N-10. ##STR47## 33.2 g TPA (0.20 mol), 100 g Glydexx N-10 (0.40mol), and 0.2 g triphenyl benzyl phosphonium chloride (TPBPC) (0.5g/mol) were charged into a 250-mL flask equipped with thermometer,stirrer, and water condenser. The mixture was heated with stirring toabout 220° C. in about one hour and kept at this temperature for 10 to20 minutes (the TPA solid phase disappeared quickly after thetemperature reached 220° C., indicating complete reaction). The materialwas poured out into a 300-mL beaker, and washed with several portions ofpetroleum ether which was added carefully with stirring. The supernatantliquid was decanted after each washing. The washed samples were thenheated to 100° C. with stirring on a heating plate in a hood to removeall the solvent. The final product XIVa was light yellow viscous liquid.ICI viscosity: 2.4 Pa.s. at 50° C., and >10 Pa.s. at 25° C. Yield was92.5%.

The diol polyester having the formula XIIIa was made by a proceduresimilar to that described in XIIIa for preparation of the non-aqueousdispersion. A second diol ester having the formula ##STR48## also wasprepared for further preparation of a non-aqueous dispersions.

Preparation of Non-Aqueous Dispersions Using Reactive Diluent XIVaDispersion of Polyester XIIIa in Reactive Diluent XIVa ##STR49##

1.0 g of polyester XIIIa and 1.0 g reactive diluent XIVa were chargedinto a glass vial (uncovered) and heated on a Bunsen burner until thepolyester XIIIa completely melted. 1.5 g toluene was added slowly,forming a homogeneous solution. The solution cooled down at roomtemperature with shaking (or with ultrasonication). Dispersion wasgradually formed during cooling. This dispersion was very stable at roomtemperature and exhibited shear thinning and thixotropic behavior.

Dispersion of Polyester XIVb+Reactive Diluent XIVa 1.0 g polyester XIVb+1.0 g reactive diluent agent ##STR50##

1.0 g of polyester XIVb and 1.0 g of reactive diluent XIVa were chargedinto a glass vial (uncovered) and heated on a Bunsen burner until thepolyester completely melted. 2.0 g xylene was added slowly, forming ahomogeneous solution. 1.0 g HMMM was then dissolved in the solution. Thesolution was well shaken while cooling down at room temperature.Dispersion was gradually formed during cooling. This dispersion was verystable at room temperature and exhibited shear thinning and thixotropicbehavior.

Clear Coatings

Formulated coatings were prepared with similar procedure as describedabove. The formulated coatings were cast as films on a 1,000 Bonderitesteel panel and baked in an oven at 150° C. for 30 minutes.

    ______________________________________                                        Formulation 1:                                                                             Polyester XIIIa                                                                              1.0 g                                                          Reactive diluent XIVa                                                                        1.0 g                                                          HMMM           1.0 g                                                          Toluene        1.5 g                                                          p-TSA          0.006 g                                           Film properties:                                                                           Tukon hardness 10.0 KHN                                                       Pencil hardness                                                                              3H/4H                                                          Reverse impact 160 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     glossy, no defect                                 Formulation 2:                                                                             Polyester XIIIa                                                                              1.0 g                                                          Reactive diluent XIVa                                                                        1.5 g                                                          HMMM           1.5 g                                                          Toluene        1.5 g                                                          p-TSA          0.006 g                                           Film properties:                                                                           Tukon hardness 10.0 KHN                                                       Pencil hardness                                                                              3H/4H                                                          Reverse impact 120 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     glossy, no defect                                 Formulation 3:                                                                             Polyester XIIIa                                                                              1.5 g                                                          Reactive diluent XIVa                                                                        1.0 g                                                          HMMM           1.0 g                                                          Toluene        2.5 g                                                          p-TSA          0.006 g                                           Film properties:                                                                           Tukon hardness 12.0 KHN                                                       Pencil hardness                                                                              4H/5H                                                          Reverse impact 160 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     glossy, but                                                                   poor leveling                                     Formulation 4 (cross-linked by polyisocyanate):                                            Polyester XIIIa                                                                              1.0 g                                                          Reactive diluent XIVa                                                                        1.5 g                                                          Mondur CB-60   2.5 g                                                          Toluene        1.5 g                                                                        150° C./                                                                        90° C./                                                       30 min.  2/hrs.                                    Film properties:                                                                           Tukon hardness                                                                              18.0 KHN 18.0 KHN                                               Pencil hardness                                                                             4H/5H    4H/5H                                                  Reverse impact                                                                              160 in-lbs.                                                                            160 in-lbs.                                            Direct impact 160 in-lbs.                                                                            160 in-lbs.                                            Film thickness                                                                              1.0 mil  1.0 mil                                                Appearance    glossy,  fuzzy-                                                               no defects                                                                             looking                                   ______________________________________                                    

Pigmented Coatings

Polyester XIIIa and the reactive diluent XIVa were charged into a 300-mLaluminum can. The polyester was melted by heating on a Bunsen burnerwith care. Half of the calculated amount of toluene was added, followedby the HMMM and an AB dispersant, Elvacite AB-1040. While cooling downat room temperature, the ingredients were shook until the transparentmaterial became a milky dispersion. A TiO₂ white pigment from du Pont,Tipure R-960, and p-TSA were added. The formulated coating was dispersedon a high speed dispersing mill for 30 minutes. The second half of thetoluene was added during the dispersing. The formulated coatingcomposition exhibited thixotropic behavior.

The formulated coating compositions were cast as a film on a 1,000Bonderate steel panel and baked at 150° C. for 30 minutes(Formulation 1) or 10 minutes (Formulation 3, with more catalyst added).

    ______________________________________                                        Formulation 1:                                                                            Polyester XIIIa                                                                              30.0 g                                                         Reactive diluent XIIa                                                                        30.0 g                                                         HMMM           30.0 g                                                         Tippure R-960  48.0 g                                                         Toluene        90.0 g                                                         p-TSA          0.30 g                                                         Elvacite AB-1040                                                                             3.60 g                                                         Byk-020 (defoamer                                                                            1 drop                                                         from Mallinckrodt)                                                Film properties:                                                                          Tukon hardness 10.0 KHN                                                       Pencil hardness                                                                              6H/7H                                                          Reverse impact  40 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     no evident defects,                                                           medium gloss                                       Formulation 2:                                                                            Polyester XIIIa                                                                              10.0 g                                                         Reactive diluent XIIa                                                                        20.0 g                                                         HMMM           15.0 g                                                         Tippure R-960  22.5 g                                                         Toluene        45.0 g                                                         p-TSA          0.225 g                                                        Elvacite AB-1040                                                                             3.38 g                                             Film properties:                                                                          Tukon hardness 10.0 KHN                                                       Pencil hardness                                                                              3H/4H                                                          Reverse impact  80 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     fairly glossy                                      ______________________________________                                    

EXAMPLE XV

Nonaqueous Dispersion Coatings Using A Double Ring Cycloaliphatic EsterAs A Reactive Diluent.

The LC-like polyester XIIIa of Example XIII having the structure:##STR51## and a non-LC composition (K-Flex 188 commercially availablefrom King Industry) having the structure: ##STR52## were made intononaqueous conversion coating compositions and studied as describedbelow.

Preparation of Nonaqueous Dispersion

Example 1 ##STR53## 1.0 g XIIIa and 1.0 g K-Flex 188 were charged into aglass vial (uncovered) and heated on a Bunsen burner until XIIIacompletely melted. 1.5 g toluene was added slowly, forming a homogenoussolution. The solution was cooled at room temperature with good shaking(or with ultrasonication). Dispersion was gradually formed duringcooling. After several weeks of storage, the dispersion separated into adilute top phase and a concentrated bottom phase (no solid precipitateswere observed); the solution returned to homogeneous dispersion afterminor shaking or stirring. This dispersion was very stable at roomtemperature and no change was observed 3 months after preparation. Thedispersion exhibited thixotropic behavior. Example 2 ##STR54##

1.0 g XIIIa and 1.0 g K-Flex 188 were charged into a glass vial(uncovered) and heated on a Bunsen burner until the oligoestercompletely melted. 2.0 g xylene was added slowly, forming a homogenoussolution. 1.0 g Resimene 746 was then dissolved in the solution. Thesolution was well shaken while cooling down at room temperature.Dispersion was gradually formed during cooling. This dispersion was verystable at room temperature and exhibited thixotropic behavior. No changewas observed after 3 months except that the dispersion separated into adilute top phase and a concentrated bottom phase; the phase separationdisappeared after minor shaking or stirring.

Clear Coating

A formulated coating composition was prepared with similar procedure asdescribed above. It was cast film on a 1,000 Bonderate steel panel andbaked in an over at 150° C. for 20 minutes (25° C. for 1 day and 70° C.for 2 h for Example 4).

Example 3

    ______________________________________                                        Example 3                                                                     Formulation: Polyester XIIIa                                                                              1.0 g                                                          K-Flex 188     1.0 g                                                          Resimene 746   1.0 g                                                          Xylene         1.5 g                                                          p-TSA          0.006 g                                           Film properties:                                                                           Tukon hardness 14.0 KHN                                                       Pencil hardness                                                                              4H/5H                                                          Reverse impact 160 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     glossy, no defect                                 Example 4                                                                     Formulation: Polyester XIIIa                                                                              1.0 g                                                          K-Flex 188     1.5 g                                                          Resimene 746   1.5 g                                                          Xylene         1.5 g                                                          p-TSA          0.006 g                                           Film properties:                                                                           Tukon hardness 12.0 KHN                                                       Pencil hardness                                                                              3H/4H                                                          Reverse impact 160 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     glossy, no defect                                 Example 5                                                                     Formulation: Polyester XIIIa                                                                              1.5 g                                                          K-Flex 188     1.0 g                                                          Resimene 746   1.0 g                                                          Xylene         2.5 g                                                          p-TSA          0.006 g                                           Film properties:                                                                           Tukon hardness 15.0 KHN                                                       Pencil hardness                                                                              4H/5H                                                          Reverse impact 120 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     glossy, but                                                                   poor leveling                                     Example 6 (cross-linked by an isocyanate prepolymer)                          Formulation: Polyester XIIIa                                                                              1.0 g                                                          K-Flex 188     1.5 g                                                          Mondur CB-60   2.5 g                                                          Dibutyltin dilaurate                                                                         0.008 g                                                        Toluene        1.5 g                                                                        25° C./                                                                         70° C./                                                       1 day    2 hrs.                                    Film properties:                                                                           Tukon hardness                                                                              16.0 KHN 20.0 KHN                                               Pencil hardness                                                                             3H/4H    4H/5H                                                  Reverse impact                                                                              160 in-lbs.                                                                            160 in-lbs.                                            Direct impact 160 in-lbs.                                                                            160 in-lbs.                                            Film thickness                                                                              1.0 mil  1.0 mil                                                Appearance    glossy,  fuzzy-                                                               no defect                                                                              looking                                   ______________________________________                                    

Pigmented Coatings Cross-linked by HMMM

Polyester XIIIa and K-Flex 188 were charged into a 300 mL aluminum canand were melted by heating on a Bunsen burner with care. Half of thecalculated amount of xylene was added, followed by Resimene 746 andElvacite AB-1040. While cooling down in the atmosphere, the solution waskept shaking until the transparent material became a milky dispersion.Tipure R-960 and p-TSA were added. The coating composition was dispersedon a high speed dispersing mill for 30 minutes. The second half of thexylene was added during the dispersing. The formulated coatingcomposition was very stable; no phase separation was observed after 3months. The formulated coating composition exhibited thixotropicbehavior.

The formulated coating compositions were cast film on a 1,000 Bonderatesteel panel and baked at 150° C. for 20 minutes.

Example 7

    ______________________________________                                        Example 7                                                                     Formulation:                                                                              Polyester XIIIa 10.5 g                                                        K-Flex 188      10.0 g                                                        HMMM (Resimene 746)                                                                           10.0 g                                                        TiO.sub.2 White Pigment                                                                       15.0 g                                                        (Tipure R-960)                                                                Xylene          30.0 g                                                        p-TSA           0.15 g                                                        Dispersant      2.00 g                                                        (Elvacite AB-1040)                                                            Defoamer (Byk-020)                                                                            1 drop                                            Film properties:                                                                          Tukon hardness  14.0 KHN                                                      Pencil hardness 7H                                                            Reverse impact   80 in-lbs.                                                   Direct impact   160 in-lbs.                                                   Film thickness  0.7 mil                                                       Appearance      med. gloss, some                                                              pinholing                                         Example 8                                                                     Formulation:                                                                              Polyester XIIIa 10.0 g                                                        K-Flex 188      20.0 g                                                        Resimene 746    15.0 g                                                        Tippure R-960   22.5 g                                                        Toluene         40.0 g                                                        p-TSA           0.23 g                                                        Elvacite AB-1040                                                                              3.38 g                                                        Byk-020         2 drops                                           Film properties:                                                                          Tukon hardness  12.0 KHN                                                      Pencil hardness 7H                                                            Reverse impact   80 in-lbs.                                                   Direct impact   160 in-lbs.                                                   Film thickness  1.0 mil                                                       Appearance      glossy                                            ______________________________________                                    

Pigmented Coatings Cross-linked by an Isocyanate Prepolymer.

Polyester XIIIa and K-Flex 188 were charged into a 300 mL aluminum canand were melted by heating on a Bunsen burner with care. Half of thecalculated amount of toluene was added, followed by Mondur CB-60 andElvacite AB-1040. While cooling down at room temperature, the solutionwas kept shaking until the transparent material became a milkydispersion. Tipure R-960, Byk-020, and dibutyltin dilaurate were added.The paint was dispersed on a high speed dispersing mill for 30 minutes.The second half of the toluene was added during the dispersing. Theformulated coating composition was very stable; no phase separation wasobserved. The formulated coating composition exhibited thixotropicbehavior.

The formulated coating compositions were cast film on a 1,000 Bonderatesteel panel and baked at 70° C. for 2 h.

Example 9

    ______________________________________                                        Example 9                                                                     ______________________________________                                        Formulation:  Polyester XIIIa                                                                              10.0 g                                                         K-Flex 188     20.0 g                                                         Mondur CB-60   30.0 g                                                         Tipure R-960   22.5 g                                                         Toluene        30.0 g                                                         p-TSA          0.23 g                                                         Dibutlyltin dilaurate                                                                        0.18 g                                                         Elvacite AB-1040                                                                             3.00 g                                                         Byk-020        2 drops                                          Film properties:                                                                            Tukon hardness 22.0 KHN                                                       Pencil hardness                                                                              7H                                                             Reverse impact  80 in-lbs.                                                    Direct impact  160 in-lbs.                                                    Film thickness 1.0 mil                                                        Appearance     fairly glossy                                    ______________________________________                                    

EXAMPLE XVI

Properties as to viscosity, yield stress and sagging were studied as tothe following compounds--

A LC-like Composition (a) having the formula ##STR55## which waspreviously described in connection with polyester VC of Example V;

A LC-like Composition (b) having the formula ##STR56## which waspreviously described in connection with polyester VC of Example V;

A LC-like Composition (c) having the formula ##STR57## and which waspreviously described in connection with polyester VIIF;

A nonliquid crystalline Composition (d) having the formula ##STR58##which was generally described in connection with polyester XIII C;

A LC-like Composition (e) having the formula ##STR59## which compositionwas generally described in Example V.

A nonliquid crystalline Composition (f) having the general formula##STR60## which was generally described in Example XIV; and

A nonliquid crystalline Composition (g) K-Flex 188 (non-LC; commercialproduct from King Industry) which has the general formula ##STR61## and

A nonliquid crystalline Composition (h) which has the general formula##STR62##

Temperature Dependence of the Viscosity of the LC-Like Oligomers

The viscosity of the LC polymers was determined with an ICI viscometerat several temperatures from 25° to 150° C. For thixotropic samples, thesteady viscosity was recorded. Tables 6-9 show the viscosity vs.temperature for several LC polymers.

                  TABLE 6                                                         ______________________________________                                        Viscosity vs. Temperature for Composition (a)                                 Temperature (°C.)                                                                25    50       75   100    125  150                                 ______________________________________                                        Viscosity (poise)                                                                             1.25     1.00 0.45   0.85 0.45                                (heating)                                                                     Viscosity (poise)                                                                             0.70     0.20 1.40   0.82 0.45                                (cooling)                                                                     ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Viscosity vs. Temperature for Composition (b)                                 Temperature (°C.)                                                                 50     75      100  (115)* 125  150                                ______________________________________                                        Viscosity (poise)                                                                        >100   1.5     0.4  46.0   2.5  1.2                                (heating)                                                                     Viscosity (poise)                                                                        >100   1.5     0.6  12.0   2.5  1.1                                (cooling)                                                                     ______________________________________                                         *Estimated temperature.                                                  

                  TABLE 8                                                         ______________________________________                                        Viscosity vs. Temperature for Composition (c)                                 Temperature (°C.)                                                                 25     50       75   100   125  150                                ______________________________________                                        Viscosity (poise)                                                                        >100   34.0     >100 29.5  7.5  1.5                                (heating)                                                                     Viscosity (poise)                                                                        >100   89.5     >100 36.5  9.0  1.5                                (cooling)                                                                     ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        Viscosity vs. Temperature for Composition (e)                                 Temperature (°C.)                                                                 25     50       (65)*                                                                              75    100  125                                ______________________________________                                        Viscosity (poise)                                                                        >100   12.0          15.5  2.0  0.2                                (heating)                                                                     Viscosity (poise)                                                                        45     2.0      57.0 16.2  2.5  0.1                                (cooling)                                                                     ______________________________________                                         *Estimated temperature.                                                  

It is seen from Tables 6-7 of this Example that for the LC-likepolyesters the viscosity first decreases and then increases withincreasing temperature until a maximum. While not intending to be boundby any theory, the unusual rheological behavior has been explained asfollows. In the LC state, the polymers are oriented and may exhibit muchlower viscosity than nonoriented polymers. With increase of temperature,the polymers become isotropic and the viscosity increases dramatically.On the other hand, there is a general tendency for the viscosity ofpolymers to decrease upon increasing temperature due to thermal motion.The results of these competing effects lead to a maximum viscosity uponincreasing temperature. Alternate explanations, however, are possible.

The LC-like polymers of the invention were compared with the non-LCcounterparts. The viscosity of several non-LC polymers with similarstructures to the LC-like polymers of the invention was measured. Tables10 and 11 of this Example show the temperature dependence of Composition(d) and Composition (h) (non-LC counterparts of Composition (c) andComposition (a) respectively). It is seen that the viscosity decreasessteadily with increasing temperature, in contrast to the unusualviscosity behavior of the LC-like polymers.

                  TABLE 10                                                        ______________________________________                                        Viscosity vs. Temperature for                                                 Composition (d) (non-LC)                                                      Temperature (°C.)                                                                 25     50       75   100   125  150                                ______________________________________                                        Viscosity (poise)                                                                        >100   >100     >100 29.0  7.5  1.5                                (heating)                                                                     Viscosity (poise)                                                                        >100   >100     >100 28.0  5.4  1.8                                (cooling)                                                                     ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        Viscosity vs. Temperature for                                                 Composition (h) (non-LC)                                                      Temperature (°C.)                                                                 25     50       75   100   125  150                                ______________________________________                                        Viscosity (poise)                                                                        >100   24.5     2.2  0.5   0.1  0.1                                (heating)                                                                     Viscosity (poise)                                                                        >100   28.5     2.4  0.5   0.1  0.1                                (cooling)                                                                     ______________________________________                                    

Thixotropic Behavior of LC-Like Polymers

Table 12 of this Example shows the time dependence of the ICI viscosityof Composition (c) at different temperatures. The viscosity in theLC-like region (around 50° C.) decreases with time to a steady value,indicating thixotropic properties of the LC-like polymers. The viscositydecrease is possibly due to break-up of certain structure (possibly LCassociation) with time.

                  TABLE 12                                                        ______________________________________                                        Viscosity vs. Shear Time of Composition (c) at Different Temperature.         Temperature (°C.)                                                                   Visc. (poise)/Shearing Time (second)                             ______________________________________                                         25          >100/0  >100/30    --   --                                        50          >100/0  30/26      20/60                                                                              20/120                                    75          >100/0  100/30     --   --                                       100             48/0 48/30      48/60                                                                              48/120                                   125             13/0 13/30      13/60                                                                              13/120                                   150             4/0   4/30       4/60                                                                               4/120                                   ______________________________________                                    

Yield Stress of LC-Like Polymers

The yield stress was determined by measuring the relative flow distanceof the polymers at different temperatures. 0.2 g of sample was placed onan aluminum panel sitting at 45° angle and the flow distance of theoligomers after 10 minutes was recorded.

                  TABLE 13                                                        ______________________________________                                        Flow Distance of Composition (c) At Different Temperatures                    Temperature (°C.)                                                                      25      50    60    90  150                                   ______________________________________                                        Flow distance (cm)/10 min.                                                                    0.0     0.0   6.4   6.0 9.5                                   ______________________________________                                    

Table 12 of this Example shows the flow distance of Composition (c)after 10 minutes at different temperatures. Although the polymer isviscous liquid or semi-solid at room temperature, no flow was observedup to 50° C., indicating yield stress of the polymer below about 50° C.At 60° C. and above, Composition (c) flowed, indicating zero yieldstress. Since the transition temperature of Composition (c) is 43.0(T_(m)) and 59.0° C. (T_(c)) (FIG. 4), the flow distance data suggestthat the yield stress is possibly due to LC association.

Sagging Resistance of Coatings Formulated from LC-Like Polymers.

Testing Methods

The method of ASTM 4400 was used except that an aluminum panel insteadof a chart was used because of higher baking temperature. The sample wascast on an aluminum panel using Leneta anti-sag meter (The LenetaCompany), and the panel was set 90° to the horizontal direction at thetesting temperature for a designated time (such as 20 minutes). Thethickness of the thickest unsagged strip was recorded as theanti-sagging value.

Sagging Resistance of Solvent Coatings at Elevated Temperature

Example 1 (LC)

    ______________________________________                                        Formulation:                                                                           Composition (c)      2.5     g                                                HMMM (Resimene 746)  0.5     g                                                Para toluene Sulfonic acid (p-TSA)                                                                 0.006   g                                                Xylene               2.0     g                                                p-TSA                0.006   g                                       ______________________________________                                    

Baking conditions: 150° C. for 20 minutes. Sagging Resistance: 6 mil.Appearance of coating: glossy.

Example 2 (Non-LC counterpart of Example 1)

    ______________________________________                                        Formulation:  Composition (d)                                                                           2.5       g                                                       Resimene 746                                                                              0.5       g                                                       p-TSA       0.006     g                                                       Xylene      2.0       g                                         ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 3 mil.Appearance of coating: glossy.

Example 3 (LC)

    ______________________________________                                        Formulation:  Composition (e)                                                                           2.0       g                                                       Resimene 746                                                                              1.0       g                                                       p-TSA       0.006     g                                                       Xylene      2.0       g                                         ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 10 mil.Appearance of coating: glossy.

Example 4 (LC)

Formulation: Composition (c) 1.5 g

    ______________________________________                                        Formulation:                                                                          Composition (c)         1.5    g                                              Polyisocyanate based upon toluene diisocyanate                                                        1.9    g                                              blocked with ε-Caprolactam (Desmodur BL-                              1185A from Mobay Corporation)                                                 Dibutyltin dilaurate    0.007  g                                              Toluene                 1.0    g                                      ______________________________________                                    

Curing condition: 70° C. for 1 h. Sagging Resistance: 12 mil. Appearanceof coating: glossy.

Sagging Resistance of Solvent Coatings at Room Temperature

Example 5 (LC)

    ______________________________________                                        Formulation: Composition (c)                                                                            2.5       g                                                      Mondur CB-60 1.6       g                                                      Dibutyltin dilaurate                                                                       0.008     g                                                      Toluene      2.0       g                                         ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: 10mil. Appearance of coating: glossy.

Example 6 (Non-LC) counterpart of Example 4

    ______________________________________                                        Formulation: Composition (c)                                                                            2.5       g                                                      Mondur CB-60 1.6       g                                                      Dibutyltin dilaurate                                                                       0.008     g                                                      Toluene      2.0       g                                         ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: <3mil. Appearance of coating: glossy.

Sagging Resistance of LC-Like Nonaqueous Dispersion Coatings at ElevatedTemperature

Example 7 (LC)

    ______________________________________                                        Formulation:  Composition (a)                                                                           1.0       g                                                       Composition (f)                                                                           1.0       g                                                       Resimene 746                                                                              1.0       g                                                       p-TSA       0.006     g                                                       Xylene      1.5       g                                         ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 12 mil.Appearance of coating: glossy.

Example 8 (Non-LC)

    ______________________________________                                        Formulation: Composition (f)                                                                            2.0       g                                                      Resimene 746 1.0       g                                                      p-TSA        0.006     g                                                      Xylene       2.0       g                                         ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: <3 mil.Appearance of coating: glossy.

Example 9 (LC)

    ______________________________________                                        Formulation:                                                                             Composition (a)  1.0      g                                                   Composition (g) (K-Flex 188)                                                                   1.0      g                                                   Resimene 746     1.0      g                                                   p-TSA            0.006    g                                                   Xylene           1.5      g                                        ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 12 mil.Appearance of coating: glossy.

Example 9 (Non-LC counterpart of Example 9)

    ______________________________________                                        Formulation:                                                                             Composition (g) (K-Flex 188)                                                                   2.0      g                                                   Resimene 746     1.0      g                                                   p-TSA            0.006    g                                                   Xylene           2.0      g                                        ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: <3 mil.Appearance of coating: glossy.

Sagging Resistance of Nonaqueous LC-Like Dispersion Coatings Cured atRoom Temperature

Example 11 (LC)

    ______________________________________                                        Formulation: Composition (a) 1.0    g                                                      Composition (f) 1.5    g                                                      Dibutyltin dilaurate                                                                          0.008  g                                                      Mondur CB-60    2.5    g                                                      Toluene         1.5    g                                         ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: 12mil. Appearance of coating: fairly glossy.

Example 12 (Non-LC counterpart of Example 18)

    ______________________________________                                        Formulation: Composition (f) 2.5    g                                                      Mondur CB-60    2.5    g                                                      Dibutyltin dilaurate                                                                          0.008  g                                                      Toluene         2.0    g                                         ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: <3mil. Appearance of coating: glossy.

Example 13 (LC)

    ______________________________________                                        Formulation:                                                                             Composition (a)  1.3      g                                                   Composition (g) (K-Flex 188)                                                                   1.2      g                                                   Dibutyltin dilaurate                                                                           0.008    g                                                   Mondur CB-60     2.5      g                                                   Toluene          1.5      g                                        ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: 10mil. Appearance of coating: fairly glossy.

Example 14 Non-LC counterpart of Example 20)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (g)       2.5    g                                                (K-Flex 188)                                                                  Mondur CB-60          2.5    g                                                Dibutyltin dilaurate  0.008  g                                                Toluene               2.0    g                                                ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: <3mil. Appearance of coating: glossy.

Improved Sag Resistance of Composition (c) (Soluble LC-Like) Coatingswith Addition of Composition (a) (Insoluble LC)

Example 15 (Soluble LC, the same as Exam 1)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (c)       2.5    g                                                Resimene 746          0.5    g                                                p-TSA                 0.006  g                                                Xylene                2.0    g                                                ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 6 mil.Appearance of coating: glossy.

Example 16 Addition of Composition (a) into Composition (c))

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (c)       1.8    g                                                Composition (a)       0.2    g                                                Resimene 746          1.0    g                                                p-TSA                 0.006  g                                                Xylene                2.0    g                                                ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 8 mil.Appearance of coating: glossy.

Example 17 (Addition of Composition (a) into Composition (c))

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (c)       1.2    g                                                Composition (a)       0.8    g                                                Resimene 746          1.0    g                                                p-TSA                 0.006  g                                                Xylene                2.0    g                                                ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 12 mil.Appearance of coating: glossy.

Sagging Resistance of Pigmented Coatings at Elevated Temperature

Example 18 (LC)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (c)       30.0   g                                                Resimene 746          15.0   g                                                TiO.sub.2 White Pigment                                                                             22.5   g                                                (Tipure R-960                                                                 from du Pont)                                                                 p-TSA                 0.23   g                                                Xylene                40.0   g                                                Dispersant            3.4    g                                                (Elvacite AB-1040)                                                            Defoamer (Byk-020)    2      drops                                            ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 10 mil.Appearance of coating: glossy.

Example 19 (LC)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (c)      20.0   g                                                 Resimene 746         10.0   g                                                 Tipure R-960         26.7   g                                                 p-TSA                0.17   g                                                 Toluene              40.0   g                                                 Elvacite AB-1040     2.0    g                                                 Byk-020              1      drop                                              ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 12 mil.Appearance of coating: fairly glossy.

Example 20 (LC)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (a)      30.0   g                                                 Composition (f)      40.00  g                                                 Resimene 746         30.0   g                                                 Tipure R-960         48.0   g                                                 p-TSA                0.03                                                     Xylene               90.0   g                                                 Elvacite AB-1040     3.6    g                                                 Byk-020              1      drop                                              ______________________________________                                    

Baking condition: 150° C. for 20 minutes. Sagging Resistance: 12 mil.Appearance of coating: fairly glossy.

Example 21 (LC)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (a)      10.03  g                                                 Composition (g)      20.0   g                                                 (K-Flex 188)                                                                  Resimene 746         10.00  g                                                 Tipure R-960         15.00  g                                                 p-TSA                0.15   a                                                 Xylene               30.0   g                                                 Elvacite AB-1040     2.0    g                                                 ______________________________________                                    

Baking condition: 150° C. for 30 minutes. Sagging Resistance: 12 mil.Appearance of coating: fairly glossy.

Sagging Resistance of Pigmented Coatings at Lower or Room Temperature

Example 22 (LC)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (c)       16.0   g                                                Mondur CB-60          14.0   g                                                Dibutyltin dilaurate  0.05   g                                                Tipure R-960          20.0   g                                                Toluene               20.0   g                                                Elvacite AB-1040      1.4    g.                                               Byk-020               1      drop                                             ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: 12mil. Appearance of coating: glossy.

Example 23 (LC)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (e)       26.3   g                                                Mondur CB-60          22.6   g                                                Dibutyltin dilaurate  0.18   g                                                Tipure R-960          39.2   g                                                Toluene               60.0   g                                                Elvacite AB-1040      3.0    g.                                               Byk-020               1      drop                                             ______________________________________                                    

Curing condition: room temperature for 1 day. Sagging Resistance: 12mil. Appearance of coating: glossy.

Example 24 (LC)

    ______________________________________                                        Formulation:                                                                  ______________________________________                                        Composition (a)       5.0    g                                                Composition (f)       10.0   g                                                Mondur CB-60          15.0   g                                                Dibutyltin dilaurate  0.05   g                                                Tipure R-960          20.0   g                                                Toluene               2.0    g                                                Elvacite AB-1040      1.4    g.                                               Byk-020               1      drop                                             ______________________________________                                    

Curing condition: 70° C. for 12 h. Sagging Resistance: 12 mil.Appearance of coating: glossy.

Although the invention has been described with regard to its preferredembodiments, it should be understood that various changes andmodifications as would be obvious to one having the ordinary skill inthis art may be made without departing from the scope of the inventionwhich is set forth in the claims appended hereto.

EXAMPLE XVII

Synthesis of water reducible oligoester derived fromdimethlterephthalate with decanediol; coating formulation.

    ______________________________________                                                       Weight used, g                                                                            Mole ratio                                         ______________________________________                                        Step 1.                                                                       Decanediol       130.0         1.5                                            Dimethylterephthalate                                                                          97.0          1.5                                            Zinc acetate     0.456         0.2% total                                                                    weight                                         Step 2.                                                                       Oligoester (from step 1)                                                                       65.0          1                                              Trimellitic anhydride (TMA)                                                                    3.46          0.3                                            Butyl Cellosolve 13.7          --                                             Dimethylethanolamine                                                                           6.0           --                                             Water            67.06         --                                             ______________________________________                                    

Step 1: Into a 0.5-L three-neck flask equipped with stirrer, condenser,Dean-Stark trap, thermometer and N₂ gas inlet tube were placed thematerials of Step 1. The reaction mixture was stirred and heated underN₂ to 150° C. and then kept at this temperature for 1 hour. CH₃ OH wasremoved by distillation. After 1 hour the temperature was increased to230° C.; 90% of theoretical amount of CH₃ OH was collected in theDean-Stark strap during 5 hours. The reaction material was cooled toabout 90° C. and toluene was added. The hot solution was poured into thebeaker and cooled to 25° C.; the precipitate which separated wascollected, dissolved in CH₂ Cl₂, reprecipitated by addition of CH₃ OH,and washed with CH₃ OH. The solid was collected and dried in oven at120° C. overnight; yield was about 78%.

Step 2. The solid from Step 1 was placed in to 250-mL three-neck flaskequipped with stirrer, condenser, thermometer and N₂ gas inlet tube. Theoligoester was heated to about 175° C. and N₂ gas flow, and TMA wasadded. The reaction mixture had an acid number of about 50 mg KOH/g. Theresulting oligomer was stirred at 170°-180° C. for about 30 minutes andcooled to 130° C. Dimethylethanolamine (2 eq. per mole of trimelliticanhydride) was added at 130° C. and then butyl cellosolve was added. Themixture was stirred at 90°-100° C. for 0.5 hour, and water was added toproduce an aqueous dispersion which was used without purification; NVWwas determined after 2 hours drying at 120° C.

Coating formulation: The enamel binder was formulated at anoligoester/HMMM/P-TSA weight ratio of 70/30/0.3 and was pigmented at apigment/binder ratio 0.7 with a TiO₂ pigment. Dow Corning paint additive57# and BYK 020 were used at 0.1% of total paint weight to preventfoaming, and help leveling and DuPont Elvacite AB⁺ dispersant (2% ofpigment weight) was used to help stabilize the TiO₂. The solvent used inthe paint formulation was butyl cellosolve and water. Pigment dispersionwas performed on a high speed disk disperser. But the final grindcorresponded to a Hegman value of about 4. The paint exhibited athixotropic nature.

Coatings properties: The coating was drawn down with a wire-wound bar onsteel panels and was baked for 20 minutes at 175° C. The baked coatingshad discernable ridges and valleys. Poor leveling was attributed to thethixotropic rheology of the liquid coating. The cured coating had thefollowing film properties.

    ______________________________________                                        Reverse impact   160                                                          resistance, in-lb                                                             Hardness, Knoop   28                                                          Solvent resistance,                                                                            200                                                          acetone double rubs                                                           ______________________________________                                    

EXAMPLE XVIII

Rheological Behavior Study On LC-Like Oligomers.

The six compositions studied were:

1. "K-Flex" 188, a commercial reactive diluent sold by King Industries.It is an isotropic liquid. (See Table I)

2. "Resimene 747" a monomeric HMMM type melamine resin sold by Monsanto.It is also isotropic. (See Table II)

3. A blend of 10GT (decanediol terephthalate Composition (b), m=2), asdescribed in Examples XVI and V, with K188 (50/50 w/w). This is a blendof LC-like 10GT with isotropic K188. (See Table III)

4. A blend of 10GT, K188, and R-747 (1/1/1 w/w/w). This blend is acomplete 100% solids coatings binder that would cure if baked highenough. The catalyst normally used was left out to prevent reaction inthe rheometer. (See Table IV)

5. A blend of 6GT (hexanediol terephthalate, Composition (a), m=2), asdescribed in Examples XVI and V, K188, and R-747 (1/1/1 w/w/w). (SeeTable V)

6. A blend of 6 GT with K188 (50/50 w/w). (See Table VI)

Instrument: HAAKE Viscometers-Rotovisco RV 100 (HAAKE Mess-Technik GmbHu. Co., Germany) was used in this study. The temperature was at therange of 25° C. to 125° C. The shear rate was at the range of 252 s⁻¹ to25200 s⁻¹. HAAKE viscometer could not measure high viscosity at veryhigh shear rate. This is a limitation of HAAKE viscometer. Theviscosities measured by HAAKE viscometer were tabulated below.

                  TABLE I                                                         ______________________________________                                        Viscosities of K188 at a variety of temperatures.                             Viscosity (Pa*s)                                                              Shear Rate                                                                            T =      T =      T =    T =    T =                                   (s-1)   114.6° C.                                                                       88.9° C.                                                                        68.1° C.                                                                      56.7° C.                                                                      25.8° C.                       ______________________________________                                        25200   0.05     0.08     0.21   *      *                                     22680   0.04     0.08     0.22   *      *                                     20160   0.04     0.08     0.22   *      *                                     17640   0.04     0.08     0.22   *      *                                     15120   0.05     0.08     0.22   *      *                                     12600   0.06     0.08     0.23   0.41   *                                     11340   0.07     0.08     0.21   0.42   *                                     10080   0.07     0.08     0.24   0.42   *                                     6300    0.07     0.08            0.43   *                                     5040    0.08     0.09     0.22          0.71                                  2520    0.10     0.08            0.57   1.02                                  2268    0.11                     0.60   1.42                                  2016                      0.23   0.57   1.44                                  1613             0.17     0.25                                                1411             0.57     0.23                                                ______________________________________                                         *The viscosity is too high to be measurable by HAAKE viscometer.         

                  TABLE II                                                        ______________________________________                                        The viscosities of Resimene 747                                               at a variety of temperatures.                                                 Shear Rate                                                                            Viscosity (Pa*s)                                                      (s.sup.-1)                                                                            T = 110.2° C.                                                                     T = 88.4° C.                                                                     T = 56.6° C.                                                                   T = 25.7° C.                      ______________________________________                                        25200   0.03       0.05      0.18    *                                        22680   0.03       0.05      0.18    *                                        20160   0.03       0.05      0.18    *                                        17640   0.02       0.05      0.18    *                                        15120   0.02       0.05      0.18    *                                        12600   0.03       0.05      0.20    *                                        11340   0.04       0.05      0.21    *                                        10080   0.04                 0.21    *                                        8820    0.04       0.05      0.21    *                                        7560    0.04       0.05      0.22    *                                        6300    0.04                 0.22    *                                        5040               0.05      0.23    1.07                                     4536               0.05      0.22    1.06                                     4032               0.04      0.21    1.04                                     3780    0.05                                                                  3528                         0.21    0.99                                     3402    0.05                                                                  3024    0.05       0.04      0.20    0.99                                     2646    0.05                                                                  2268    0.04                                                                  1890    0.04                                                                  ______________________________________                                         *The viscosity is too high to be measurable by HAAKE viscometer.         

                                      TABLE III                                   __________________________________________________________________________    The viscosities of 10GT blended                                               with K188 (ratio 1:1 by weight).                                              Shear                                                                         Rate                                                                              Viscosity (Pa*s)                                                          (s.sup.-1)                                                                        T = 114.8° C.                                                                 T = 102.72° C.                                                                T = 94.4° C.                                                                 T = 90° C.                                                                   T = 88.4° C.                                                                 T = 83.3° C.                       __________________________________________________________________________    25200                                                                             0.05   0.10   0.12  *     0.17  *                                         22680                                                                             0.06   0.10   0.12  0.26  0.17  *                                         21420                   0.26        *                                         20160                                                                             0.06   0.10   0.12  0.28  0.18  *                                         17640                                                                             0.06   0.10   0.13  0.29  0.18  *                                         15120                                                                             0.06   0.10   0.13  0.30  0.19  *                                         12600                                                                             0.07   0.11   0.15  0.32  0.31  *                                         11340                                                                             0.07   0.11   0.16  0.33  0.32  *                                         10080                                                                             0.07   0.12   0.16  0.35  0.33  *                                         8820                                                                              0.08   0.12   0.17  0.36  0.34  *                                         7560                                                                              0.08   0.13   0.18  0.39  0.36  0.73                                      6300                                                                              0.07   0.14   0.19  0.41  0.37  0.85                                      5040                                                                              0.08   0.16   0.23  0.52  0.59  1.01                                      4536                                                                              0.07   0.16   0.24  0.56  0.61  1.08                                      4032                                                                              0.06   0.17   0.25  0.60  0.64  1.14                                      3528                                                                              0.06   0.17   0.25  0.63  0.68  1.23                                      3024                                                                              0.06   0.18   0.27  0.68  0.73  1.31                                      2016                                                                              0.11   0.27   0.37  0.91  1.24  1.64                                      1814                                                                              0.09   0.28   0.38  0.95  1.30  1.65                                      1613                                                                              0.09   0.30   0.38  0.96  1.33  1.64                                      1411                                                                              0.09   0.32   0.39  1.02  1.38  1.63                                      1209                                                                              0.09   0.35   0.38  0.76  1.42  1.61                                      __________________________________________________________________________     *The viscosity is too high to be measurable by HAAKE viscometer.         

From Table III above, the high-shear viscosities at 88° C. were lowerthan those at 90° C. The temperature of 88 degrees was the transitiontemperature from one phase to another phase. This phenomenon is LC-likebehavior. The material is shear thinning at temperatures of 102.7° C.and below, but is virtually Newtonian at 114.8° C.

                                      TABLE IV                                    __________________________________________________________________________    The viscosities of 10GT blended with K188 and                                 Resimene 747 (ratio 1:1:1 by weight).                                         Shear                                                                             Viscosity (Pa*s)                                                          Rate                                                                              T =  T =  T =  T =  T =  T =  T =                                         (s.sup.-1)                                                                        120.4° C.                                                                   92.1° C.                                                                    86.0° C.                                                                    80.0° C.                                                                    74.0° C.                                                                    63.4° C.                                                                    55.5° C.                             __________________________________________________________________________    25200                                                                             0.08 *    *    *    *    *    *                                           22680                                                                             0.07 *    *    *    *    *    *                                           20160                                                                             0.08 *    *    *    *    *    *                                           17640                                                                             0.08 0.29 *    *    *    *    *                                           16380    0.31 *    *    *    *    *                                           15120                                                                             0.09 0.29 0.35 *    *    *    *                                           14742    0.31      *    *    *    *                                           13104    0.30      *    *    *    *                                           12600                                                                             0.08      0.40 *    *    *    *                                           11466    0.30      *    *    *    *                                           11340                                                                             0.08      0.39 *    *    *    *                                           10080                                                                             0.08      0.39 0.55 *    *    *                                           9828     0.29           *    *    *                                           8820                                                                              0.08      0.38 0.54 *    *    *                                           8190     0.28           *    *    *                                           7560                                                                              0.08      0.36 0.52 0.67 *    *                                           6300                                                                              0.08      0.35 0.49 0.62 *    *                                           5040                                                                              0.09 0.34 0.41 0.59 0.71 1.08 *                                           4536                                                                              0.09 0.34 0.40 0.57 0.70 1.06 *                                           4032                                                                              0.10 0.33 0.40 0.57 0.68 1.03 *                                           3528                                                                              0.10 0.32 0.37 0.54 0.65 0.98 *                                           3024                                                                              0.11 0.32 0.36 0.49 0.61 0.91 *                                           2520          0.48      0.73      *                                           2268          0.46      0.71      *                                           2016                                                                              0.11 0.74 0.46 0.58 0.65 1.14 1.57                                        1814                                                                              0.11 0.73      0.57      1.39 1.96                                        1764          0.59      0.62                                                  1613                                                                              0.12 0.75      0.53      1.35 1.92                                        1411                                                                              0.12 0.77      0.51      1.30 1.87                                        1209                                                                              0.13 0.76      0.47      1.23 1.76                                        __________________________________________________________________________     *The viscosity is too high to be measurable by HAAKE viscometer.         

A dispersion of 10GT in K188 and R747 contains all the elements of asolventless coating binder. As shown in Table IV, such a dispersionexhibits shear thinning at temperatures (86°-92° C.) near the phasetransition temperatures of 10GT. At higher temperatures (120° C.) shearthinning is less pronounced, and at lower temperatures (74°-80° C.) thedispersions appear to have approximately Newtonian rheology. Further, atlow shear rates (less than about 2100 sec⁻¹) the dispersion exhibits atrough in its viscosity-temperature curve, the viscosity increasing from0.47 Pa.s to 0.76 Pa.s when the dispersion is heated from 80° to 92° C.Thus the unusual rheological characteristics of 10GT persist even whenthe dispersion is diluted with Newtonian cross-linker and reactivediluent. These characteristics indicate that the dispersion could beapplied as a solventless coating at temperatures of 74° to 80° C. withcommercial equipment capable of applying coatings at viscosities in therange of 0.5-0.7 Pa.s and would resist sagging when heated at least to92° C. Alternatively, it could be applied at 92° C. with equipmentcapable of applying coatings at a viscosity of about 0.3 Pa.s at shearrates above about 3,000 sec⁻¹ and would resist sagging because of itsshear thinning characteristics. Thus the unusual theologicalcharacteristics are exemplified in the following Tables.

                  TABLE V                                                         ______________________________________                                        The viscosities of 6GT blended with R747 and                                  K188 (ratio 1:1:1 by weight).                                                 Viscosity (Pa*s)                                                              Shear Rate                                                                            T =      T =      T =    T =    T =                                   (s-1)   101.4° C.                                                                       83.0° C.                                                                        70.0° C.                                                                      60.0° C.                                                                      50.0° C.                       ______________________________________                                        25200   0.11     *        *      *      *                                     22680   0.11     0.24     *      *      *                                     20160   0.11     0.23     *      *      *                                     17640   0.11     0.23     *      *      *                                     15120   0.11     0.24     *      *      *                                     12600   0.11     0.24     *      *      *                                     11340   0.11     0.25     0.49   *      *                                     10080   0.11     0.25     0.48   *      *                                     8820    0.11     0.25     0.48   *      *                                     7560    0.11     0.25     0.47   *      *                                     6300    0.10     0.25     0.46   *      *                                     5040    0.13     0.31     0.58   *      *                                     4536    0.13     0.31     0.57   1.20   *                                     4032    0.12     0.31     0.57   1.20   *                                     3528    0.12     0.32     0.57   1.21   1.50                                  3024    0.12     0.32     0.59   1.21   1.46                                  2016    0.18     0.41     0.85   1.49   1.96                                  1814    0.18     0.41     0.85   1.52   1.96                                  1613    0.19     0.43     0.87   1.56   1.96                                  1411    0.20     0.45     0.89   1.54   1.95                                  1209.9  0.20     0.45     0.95   1.52   1.99                                  ______________________________________                                         *The viscosity is too high to be measurable by HAAKE viscometer.         

                                      TABLE VI                                    __________________________________________________________________________    The viscosities of K188 blended with 6GT                                      (ratio 1:1 by weight).                                                        Shear                                                                             Viscosity (Pa*s)                                                          Rate                                                                              T =  T =  T =  T =  T =  T =  T =                                         (s.sup.-1)                                                                        106.4° C.                                                                   94.1° C.                                                                    85.8° C.                                                                    79.0° C.                                                                    75.0° C.                                                                    63.0° C.                                                                    52.0° C.                             __________________________________________________________________________    25200                                                                             0.08 0.14 0.20 *    *    *    *                                           22680                                                                             0.08 0.14 0.21 *    *    *    *                                           20160                                                                             0.09 0.15 0.21 0.28 *    *    *                                           17640                                                                             0.09 0.15 0.21 0.28 *    *    *                                           15120                                                                             0.09 0.15 0.21 0.28 *    *    *                                           12600                                                                             0.08 0.15 0.21 0.28 *    *    *                                           11340                                                                             0.07 0.15 0.21 0.28 0.48 *    *                                           10080                                                                             0.07 0.14 0.21 0.25 0.48 *    *                                           8820                                                                              0.07 0.14 0.21 0.24 0.49 *    *                                           7560                                                                              0.07 0.13 0.20 0.24 0.49 *    *                                           6300                                                                              0.06 0.13 0.19      0.50 *    *                                           5040                                                                              0.11 0.17 0.25 0.34 0.57 *                                                4536                                                                              0.11 0.16 0.25 0.34 0.58 1.21 *                                           4032                                                                              0.10 0.16 0.25 0.35 0.58      *                                           3528                                                                              0.10 0.16 0.26 0.36 0.60 1.20 *                                           3024                                                                              0.10 0.15 0.26 0.37 0.62 1.20 *                                           2016                                                                              0.15 0.21 0.32 0.47 0.82 1.40 1.74                                        1814                                                                              0.15 0.21 0.33 0.47 0.84 1.36 1.74                                        1613                                                                              0.15 0.21 0.35 0.50 0.85 1.32 1.85                                        1411                                                                              0.15 0.21 0.38 0.55 0.90 1.30 1.95                                        1209.6                                                                            0.14 0.22 0.38 0.59 0.95 1.19 1.94                                        __________________________________________________________________________     *The viscosity is too high to be measurable by HAAKE viscometer.         

As shown in Tables V and VI, rheological behavior of dispersions of 6GTin K188 and in K188 and R747 is broadly similar to that of thedispersions of 10GT discussed above. In this case the temperature rangeof greatest shear thinning behavior is lower (70° to 83° C.), and theviscosity in the approximately Newtonian temperature range (50° to 60°C.) is correspondingly higher. The trough in the viscosity-temperaturecurve was detected.

The various features of this invention which are believed new are setforth in the following claims.

We claim:
 1. An oxirane adduct of a polyester selected from the groupconsisting of a diacid polyester and a carboxylated diol polyester, thediacid polyester having a number average molecular weight of not greaterthan 10,000 and a general formula ##STR63## wherein m=1 to 20, but whenV=bond, Al'=bond, W=bond and Z=bond, m≧2 n=2 to 20, the diol polyesterhaving a number average molecular weight of not greater than 10,000 andthe general formula, wherein the oxirane adduct displays first ordertransitions at two different temperatures by differential scanningcalorimetry and wherein the oxirane adduct is the reaction product of amono-oxirane selected from the group consisting of phenylglycidyl ether,butylglycidyl ether, styrene oxide, and a glycidyl ester of amonocarboyl acid having six to twenty-two carbon atoms and the diacidpolyester of the general formula or the diol polyester of the generalformula which has been carboxylated, the oxirane adduct when blendedwith the polyester having the general formula having a number averagemolecular weight of less than 10,000 effective for providing adispersion of the blend.
 2. An oxirane adduct as recited in claim 1wherein the polyester is a diacid polyester.
 3. An oxirane adduct asrecited in claim 1 wherein the polyester is a diol polyester.
 4. Anoxirane adduct as recited in claim 1 wherein the polyester of thegeneral formula is the reaction product of an arylene monomer selectedfrom the group consisting of ##STR64## straight chain saturatedaliphatic diol or diacid having 6 to 17 carbon atoms which diol ordiacid is reactive with the arylene monomer and wherein R=alkyl having 1to 4 carbon atoms or H, R'=alkyl having 1 to 4 carbon atoms andX=halogen.
 5. An oxirane adduct as recited in claims 1, 2, 3 or 4wherein the mono-oxirane is a glycidyl ester of a monocarboxylic acidhaving six to twenty-two carbon atoms.
 6. An oxirane adduct as recitedin claims 1, 2, 3 or 4 wherein the mono-oxirane has the general formula##STR65## wherein R is an aliphatic group and the total number of carbonatoms in all three R groups is about 8 carbon atoms.
 7. An oxiraneadduct as recited in claim 1 wherein the polyester of the generalformula is a hydroxyl terminated polyester which has the formula##STR66## and wherein the hydroxyl terminated polyester has beencarboxylated to an acid value of from about 5 to about 230 before it isreacted with the mono-oxirane.
 8. An oxirane adduct as recited in claim1 wherein the polyester of the general formula is a hydroxyl terminatedpolyester which has the formula ##STR67## and wherein the hydroxylterminated polyester has been carboxylated to an acid value of fromabout 5 to about 230 before it is reacted with the mono-oxirane.
 9. Anoxirane adduct as recited in claim 1 wherein the polyester of thegeneral has the formula ##STR68##
 10. An oxirane adduct as recited inclaim 1 wherein the polyester of the general formula has the formula##STR69##
 11. A mono-oxirane capped polyester, where the polyester hasthe general formula ##STR70## wherein m=1 to 20, but when V=bond,Al'=bond, W=bond and Z=bond, m≧2 n=2 to 20, wherein a diol polyester ofthe general formula is carboxylated prior to oxirane capping, themono-oxirane capped polyester displays first order transitions at twodifferent temperatures by differential scanning calorimetry and whereinthe mono-oxirane which is used to cap the polyester is selected from thegroup consisting of phenylglycidyl ether, butylglycidyl ether, styreneoxide and a glycidyl ester of a mono-carboxyl acid having six totwenty-two carbon atoms.
 12. A mono-oxirane capped polyester as recitedin claim 11 wherein the polyester is a diacid polyester.
 13. Amono-oxirane capped polyester as recited in claim 11 wherein thepolyester is a diol polyester.
 14. A mono-oxirane capped polyester asrecited in claim 11 wherein the polyester of the general formula is thereaction product of an arylene monomer selected from the groupconsisting of ##STR71## straight chain saturated aliphatic diol ordiacid having 6 to 17 carbon atoms which diol or diacid is reactive withthe arylene monomer and wherein R=alkyl having 1 to 4 carbon atoms or H,R'=alkyl having 1 to 4 carbon atoms and X=halogen.
 15. A mono-oxiranecapped polyester as recited in claims 11, 12, 13, or 14 wherein themono-oxirane used to cap the polyester is a glycidyl ester of amonocarboxylic acid having six to twenty-two carbon atoms.
 16. Amono-oxirane capped polyester as recited in claims 11, 12, 13, or 14wherein the mono-oxirane used to cap the polyester has the generalformula ##STR72## wherein R is an aliphatic group and the total numberof carbon atoms in all three R groups is about 8 carbon atoms.
 17. Amono-oxirane capped polyester as recited in claim 11 wherein thepolyester of the general formula is a hydroxyl terminated polyesterwhich has the formula ##STR73## and wherein the hydroxyl terminatedpolyester has been carboxylated to an acid value of from about 5 toabout 230 before it is reacted with the mono-oxirane.
 18. A mono-oxiranecapped polyester as recited in claim 11 wherein the polyester of thegeneral formula is a hydroxyl terminated polyester which has the formula##STR74## and wherein the hydroxyl terminated polyester has beencarboxylated to an acid value of from about 5 to about 230 before it isreacted with the mono-oxirane.
 19. A mono-oxirane capped polyester asrecited in claim 11 wherein the polyester of the general has the formula##STR75##
 20. A mono-oxirane capped polyester as recited in claim 11wherein the polyester of the general formula has the formula ##STR76##21. An oxirane adduct of a polyester selected from the group consistingof a diacid polyester and a carboxylated diol polyester, the diacidpolyester having a number average molecular weight of not greater than10,000 and the general formula ##STR77## wherein m=1 to 20, but whenV=bond, Al'=bond, W=bond and Z=bond, m≧2 n=2 to 20, the diol polyesterhaving a number average molecular weight of not greater than 10,000 andthe general formula, wherein the oxirane adduct displays first ordertransitions at two different temperatures by differential scanningcalorimetry and is the reaction product of a mono-oxirane which is aglycidyl ester of a mono-carboxylic acid having six to twenty-two carbonatoms and the diacid polyester of the general formula or the diolpolyester of the general formula which has been carboxylated, theoxirane adduct when blended with the polyester having the generalformula having a number average molecular weight of less than 10,000effective for providing a dispersion of the blend.
 22. An oxirane adductas recited in claim 21 wherein the mono-oxirane has the general formula##STR78## wherein R is an aliphatic group and the total number of carbonatoms in all three R groups is about 8 carbon atoms.
 23. An oxiraneadduct as recited in claims 21 or 22 wherein the polyester of thegeneral formula is a hydroxyl terminated polyester which has the formula##STR79## and wherein the hydroxyl terminated polyester has beencarboxylated to an acid value of from about 5 to about 230 before it isreacted with the mono-oxirane.
 24. An oxirane adduct as recited inclaims 21 or 22 wherein the polyester of the general formula is ahydroxyl terminated polyester which has the formula ##STR80## andwherein the hydroxyl terminated polyester has been carboxylated to anacid value of from about 5 to about 230 before it is reacted with themono-oxirane.
 25. An oxirane adduct as recited in claims 21 or 22wherein the polyester of the general has the formula ##STR81##
 26. Anoxirane adduct as recited in claims 21 or 22 wherein the polyester ofthe general formula has the formula ##STR82##